CN103131020B - Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof - Google Patents
Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof Download PDFInfo
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- CN103131020B CN103131020B CN201310023758.2A CN201310023758A CN103131020B CN 103131020 B CN103131020 B CN 103131020B CN 201310023758 A CN201310023758 A CN 201310023758A CN 103131020 B CN103131020 B CN 103131020B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
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- 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
- C09B67/009—Non common dispersing agents polymeric dispersing agent
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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
- D06P1/16—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
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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
- D06P1/44—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
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Abstract
The invention discloses a carboxylic sulfonic-acid-group lignin lignin dye dispersing agent and a preparation method of the carboxylic sulfonic-acid-group lignin dye dispersing agent. According to the preparation method of the carboxylic sulfonic-acid-group lignin lignin dye dispersing agent, firstly, alkali lignin solid powder is added into water to prepare a solution, wherein the weight percentage concentration of the alkali lignin solid powder in the solution is 20-50%; then sulfonic-acid-group contained monomers and an initiator are added into the solution for a reaction for 1-2 hours at the temperature of 75-100 DEG C to obtain sulfonic-acid-group lignin; a carboxylic acid compound aqueous solution is prepared, wherein the mass concentration of a carboxylic acid compound is 10-40%, and epoxy chloropropane is added into the carboxylic acid compound aqueous solution dropwise at the pH of 4-7 and the temperature of 30-80 DEG C for a reaction for 1-3 hours to obtain a hydroxypropyl carboxylic acid compound; two intermediate products, namely the sulfonic-acid-group lignin and the hydroxypropyl carboxylic acid compound, are mixed for a copolymerization reaction for 0.5-3 hours at the pH of 8-12 and the temperature of 80-100 DEG C; and then a hydroxy ketone substance with the mass concentration of 20-30% is added for a reaction for 2-6 hours, and after the reaction is finished, a liquid product is obtained. The carboxylic sulfonic-acid-group lignin dye dispersing agent has a plurality of sulfonic acid groups, a plurality of carboxylic groups, a pretty high molecular weight, and a small quantity of phenolic hydroxyl groups, can improve dispensability of dyes and can reduce the reduction effect on azo dyes and the soilability to fibers.
Description
Technical field
The present invention relates to dye dispersant, particularly relate to a kind of carboxyl sulfonic group alkali lignin based dye dispersion agent and preparation method thereof.Specifically with alkaline process papermaking byproduct alkali lignin for raw material, prepare a kind of Lignins dye dispersant, this dye dispersant is applicable to the dispersion of the water-soluble dyes such as insoluble dyes and reactive dyestuffs such as dispersed dye.
Background technology
Dye dispersant can reduce dye granule particle diameter in the insoluble dyes attrition process processes such as dispersed dye, make dye stabilizer, be evenly dispersed in water; Dye dispersant also can stop the water-soluble dyes such as reactive dyestuffs to be assembled in water, and form comparatively even, stable dispersion liquid, therefore dye dispersant plays keying action in the processing and use procedure of commercial dye.
At present, the kind of conventional both at home and abroad dye dispersant has anionic and non-ionic type.Conventional anionic dispersing agents kind has: (1) naphthalene sulfonic salt condenses dispersion agent, at present, the more NNO of domestic application just belongs to this series products, and its advantage is little to the contamination of fiber, and the reduction destructive rate of azo dyes is lower, but heat-resistant stable is poor, single use over-all properties is poor, and raw material sources are limited, the problem that toxicity is higher, especially fossil resources is fewer and feweri, makes naphthalenesulfonate condensation compound dispersion agent production cost more and more higher.(2) poly carboxylic acid series, formed by unsaturated polyester carboxylic acid monomer and other monomer-grafted copolymerization, as acrylic acid graft copolymer dispersion agent, but cost is higher, and large-scale production and application also have any difficulty.Conventional nonionogenic tenside has polyethylene glycol type and polyol type etc.This kind of dispersion agent can double as emulsifying agent etc., but costly.(3) sulfonated lignin dye dispersant, mainly from the sulfonated derivative of alkali lignin in the sulfonated lignin in acid system paper-making pulping waste liquid and alkaline pulp black liquor, because its raw material comes in renewable resources, receive increasing concern in recent years.
Xylogen is that occurring in nature content is only second to cellulosic second largest biomass resource, and xylogen is the byproduct of paper industry simultaneously, and the xylogen presently more than 95% still directly enters rivers with " black liquor " form or burns after concentrating, and is seldom utilized effectively.Have huge economic benefit and social benefit to the development and utilization of xylogen, one of its main application is used as dye dispersant.Because Lignins application of dispersant is in extensive range, abundance, the feature such as with low cost and nontoxic, compared with similar petrochemicals, there is very strong competitive power.According to the difference of slurry digesting technoloy, industrial lignin can be divided into alkali lignin (Alkali lignin) and sulfonated lignin (Lignosulfonate).What obtain with kraft cooking is alkali lignin, is also called black liquid; What obtain with sulfurous method boiling is sulfonated lignin.Along with acid polishing produces a large amount of spent acid, waste water, the cost of process waste water is high and seriously pollutedly cause great damage to environment, therefore acid polishing abandoned gradually, and change into based on alkaline process, now, China's pulp industry is based on alkaline process, also a large amount of black liquor of pulp making by product containing alkali lignin is created thus, alkali lignin accounts for more than 90% of industrial lignin, but alkali lignin is only dissolved in strong alkali solution, the poor water-soluble application seriously limiting alkali lignin, is often drained or is burned, contaminate environment and waste resource.With the alkali lignin reclaimed in black liquid for xylogen dye dispersant prepared by raw material, there is important using value and Significance for Environment.
Sulfonated wheat-strew lignin dye dispersant to dyestuff, there is good dispersing property but also exist High Temperature Dispersion Stability can the reductibility of poor, azo dyes comparatively large, to problems such as the contamination of fiber are comparatively serious.
The general sulfonation reaction that adopts is prepared into sulfonated lignin dispersion agent at present, and method of sulfonating is normal pressure sulfomethylation method, High Temperature High Pressure sulfonation method, oxidation sulfonation method mainly.Research shows, sulfonation degree is higher, the adsorptive power of dispersion agent to dye molecule is stronger, the electrically charged increase of dye granule, the electrostatic repulsion between dyestuff increases, and makes dispersion liquid more stable, but because alkali lignin is net macromolecular structure, shielding effect is obvious, and the sulfonation degree of sulfonated lignin dispersion agent prepared by current existing technology is lower, and hydrophilic radical is less.In addition, current sulfonation reaction adopts S-WAT as sulphonating agent mostly, prepared sulfonated wheat-strew lignin dye dispersant produces a large amount of sodium sulfate because of its side reaction, and there is the problem that impurity in products is more, purity is lower, reduce dispersion agent to the stably dispersing performance of dyestuff, also increase the contamination to fiber simultaneously.
Lignin Dispersants is when processing dye abrasion and dye liquor high temperature contaminating, due to phenolic hydroxyl group in lignin structure and catechol group oxidized and become quinonoid structure, while self color is deepened, they also can interact with azoic dyestuff, dyestuff is reduced, destroy azo structure, cause dyestuff eclipsed.For solution Lignin Dispersants to the reduction problem of dyestuff, mainly reducing the content of its phenolic hydroxyl group, effectively can improve the contamination performance of Lignin Dispersants and the reductibility of azo dyes to a certain extent as adopted epoxychloropropane modified method.As US Patent No. 4001202 utilizes epoxy chloropropane to carry out end capping to the phenolic hydroxyl group of sulfonated lignin, reduce hydroxy radical content, reduce it and stain and reductibility, but still have a certain distance compared with its dispersing property and naphthalene system dispersion agent; US Patent No. 5989299 adopts trolamine, diethylamine is used by the dispersion agent of ion exchange reaction modified sodium lignosulfonate as azoic dyestuff system, utilize amine ion to suppress the reduction of azoic dyestuff in azoic dyestuff system, thus reduce the eclipsed of azoic dyestuff; US Patent No. 4444562 discloses and solves sulfonated lignin azo dyes reduction problem by adding intercalating agent (EDTA).
The lower-molecular-weight component of xylogen is also cause one of important factor of fiber contamination.In removing dispersion agent, the component of lower molecular weight can reduce contamination to fabric, improve that it is dispersed and improve thermostability.Chinese patent CN87102691A with after the sulfonation of non-wood plant alkali lignin through 80 ~ 100 mesh screen, after removing small molecules and impurity, prepare xylogen dye dispersant.Lignins dispersion agent prepared by US Patent No. 1177617 adopts ultrafiltration process except desulfonate or sulfomethylation xylogen middle-molecular-weihydroxyethyl are lower than obtained after the composition of 3000, and its dispersing property is significantly improved." chemistry of forest product and industry " the 4th phase in 2003 discloses the preparation method that modified wood sulfate-reducing conditions prepares dye dispersant, xylogen that middle recovery obtains is obtained for raw material with sulphite or alkaline process process, adopt acid out precipitator method purifying lignin, then at high temperature under high pressure after sulphite sulfonation or sulphite-formaldehyde sulfomethylation, with epoxy chloropropane, part phenolic hydroxyl group is closed again, make between lignin molecule crosslinked simultaneously, obtain modified lignin resin dye dispersant.
The molecular weight of Lignin Dispersants is larger, and the adsorptive power on dye dispersion particle is stronger, at relatively high temperatures, also not easily gets off from desorb particle surface, thus maintains thermostability and the dispersiveness of dye dispersion system.Chinese patent CN102174273A announces sodium lignosulfonate, formaldehyde and the compound (phenol, naphthols, benzylalcohol etc.) containing hydroxyl and carries out condensation reaction, obtains lignin sulfonate dye dispersant; US Patent No. 2680113, US4534771 alkali lignin sulfonation, or add formaldehyde after sulfonation and carry out aldol reaction, improve lignin molecule amount.Adopting physical partition method to remove small molecules xylogen prepares in the patent of xylogen dye dispersant, running cost is high, and small molecules xylogen is not used and causes the waste of resource, existing technology is just for single performances such as solution xylogen dye dispersant dispersiveness, reducing properties simultaneously, sulfonation degree and the molecular weight of prepared sulfonated lignin dispersion are lower, still containing more phenolic hydroxyl group, still await further raising at aspect of performances such as High Temperature Dispersion Stability energy, the reducing property to dyestuff and the contaminations to fiber.
Summary of the invention
The object of the invention is the carboxyl sulfonic group xylogen dye dispersant for existing sulfonated lignin dye dispersant high temperature dispersibility a kind of excellent property that is poor, that develop the contamination of fiber and the reductibility problem of azo dyes, this dispersion agent has excellent dispersing property to dyestuff, low to the contamination of fiber, the feature that the reductibility of azo dyes is lower, and widen the recycling approach of black liquid.
The present invention also aims to provide the method utilizing the byproduct of paper-making pulping to prepare xylogen dye dispersant.
Object of the present invention is achieved through the following technical solutions:
A preparation method for carboxyl sulfonic group xylogen dye dispersant, comprises the following steps:
(1) alkali lignin pressed powder is added to the water, be mixed with the aqueous solution that weight percent concentration is 20 ~ 50%, with alkaline conditioner adjust ph to 9 ~ 11, be warmed up to 75 ~ 100 DEG C, add containing sulfonic monomer, drip initiator, reaction 1 ~ 2h, obtains sulfonic group lignin liquor;
(2) be dissolved in water by carboxylic acid compound, be mixed with the solution that mass concentration is 10 ~ 40%, regulate pH to be 4 ~ 7, at temperature is 30 ~ 80 DEG C, add epoxy chloropropane with acid regulator, reaction 1 ~ 3h, obtains hydroxypropyl carboxylic acid cpd;
(3) by sulfonic group lignin liquor that step (1) is obtained by reacting, the hydroxypropyl carboxylic acid cpd be obtained by reacting with step (2) mixes, pH to 8 ~ 12 are regulated with alkaline conditioner, be heated to 80 ~ 100 DEG C, reaction 0.5 ~ 3h, drip mass concentration be 20 ~ 30% hydroxyl ketone thing carry out condensation end capping 2 ~ 6h, reaction terminate after obtain liquid carboxyl sulfonic group xylogen dye dispersant;
Above-mentioned raw materials is as follows with weight parts consumption:
Described alkali lignin is one or more the mixture in wood pulp alkali xylogen, bamboo alkali lignin, sahio base xylogen, bagasse alkali-lignin;
Described is one in sodium sulfanilate, sodium m-aminobenzene sulfonate, methylpropene sodium sulfonate, sodium allyl sulfonate, chloroethyl sodium sulfonate containing sulfonic monomer;
Described initiator is the one in ammonium persulphate, Sodium Persulfate, Potassium Persulphate;
Described carboxylic acid compound is one or both in sodium formiate, sodium acetate, sodium acrylate, sodium oxalate, Trisodium Citrate;
Described hydroxyl ketone thing is one or more mixture of otan, alpha-alcohol ketone, 3-hydroxy-2-butanone, hydroxy acetophenone, 2-hydroxy-2-methyl-5-hexanone.
For realizing the object of the invention further, described step (2) temperature of reaction is preferably 30 ~ 50 DEG C.In step (3), the polycondensation end capping time is preferably 2 ~ 4h.Described acid regulator is preferably sulfuric acid or hydrochloric acid.The mass concentration of described sulfuric acid or hydrochloric acid is preferably 10%.Described alkaline conditioner is preferably the aqueous solution of sodium hydroxide or potassium hydroxide.The aqueous solution mass concentration of described sodium hydroxide or potassium hydroxide is preferably 30%.
A kind of carboxyl sulfonic group lignin-base dye dispersant, by any one preparation of aforesaid method, its sulfonic content is greater than 2.00mmol/g, and carboxyl-content is greater than 2.0mmol/g, and content of phenolic hydroxyl groups is less than 0.5mmol/g, and molecular weight is greater than 10000Da.
The present invention compared with prior art tool has the following advantages and effect:
Prepared by the present invention has following feature containing carboxyl sulfonic group lignin-base dye dispersant:
1) the lignin-base dye dispersant that prepared by the technology of the present invention accesses carboxyl and sulfonic group hydrophilic functional group on the hydrophobic framework phenylpropyl alcohol alkyl structure unit of alkali lignin, dispersion agent phenyl ring and dye molecule can be made to produce π-π interact, hydrophilic group is soluble in water, dye granule adsorbs, thus produce larger effective Coulomb repulsion and sterically hindered effect, therefore there is excellent disperse and grind aid performance.
2) the present invention utilizes hydroxypropyl carboxylic acid sodium and sulfonic group alkali lignin to carry out graft copolymerization, not only increases the content of carboxyl, has certain sealing process to the phenolic hydroxyl group in lignin structure; Hydroxyl ketone thing is adopted to carry out polycondensation end capping to alkali lignin, not only improve the molecular weight of dispersion agent, close again the phenol type structure in lignin structure, reduce the reductive action of xylogen azo dyes and the contamination of fiber, improve the over-all properties of dispersion agent.
3) weight-average molecular weight of carboxyl sulfonic group xylogen dye dispersant that prepared by the present invention is greater than 10000Da, sulfonation degree is greater than 2.0mmol/g, carboxyl-content is greater than 2.0mmol/g, its sulfonation degree and molecular weight all show higher than the sulfonated wheat-strew lignin product of traditional technology with from the sodium lignosulfonate in acid polishing effluent, introduce the carboxyl of certain content simultaneously, there is higher negative charge density, the grinding efficiency of dyestuff can be significantly improved, improve dispersion effect to insoluble dispersed dye.
4) the technology of the present invention adopts condensation closed-end technology, significantly reduces the content of phenolic hydroxyl groups of xylogen, and the content of phenolic hydroxyl groups of the product of preparation, lower than being less than 0.5mmol/g, significantly reduces the reduction of azo dyes and the contamination to fiber.
5) existing dye dispersant is petroleum chemicals as naphthalenesulfonate formaldehyde condensation compound main raw material, and have certain toxicity, cost is higher.Main raw material alkali lignin in the technology of the present invention comes from alkaline process byproduct, belongs to green renewable resources, abundant raw material source, environment-protecting asepsis, is also the recycling to waste, is significant to energy-saving and emission-reduction, protection of the environment.In addition production technique of the present invention less than 100 DEG C at ambient pressure, compared with naphthalene system dispersion agent, synthesis technique is simple, production cost is low.
6) product prepared of the present invention is compared with naphthalene sulfonic dipersant, structurally except containing except sulfonic group, also add carboxyl, and molecular weight is comparatively large simultaneously, more excellent than naphthalene sulfonic dipersant to the High Temperature Disperse performance of dyestuff.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of embodiment 1 product and wood pulp alkali xylogen.
Fig. 2 is embodiment 1 product and wood pulp alkali xylogen
1h-NMR spectrogram.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is further illustrated, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Be added to the water by 100g wood pulp alkali xylogen pressed powder, stir the NaOH aqueous solution adjust ph to 9 that lower mass percent concentration is 30%, melt into mass concentration is the solution of 20%; Add 10g sodium sulfanilate at being warming up to 75 DEG C, drip 1g ammonium persulphate, reaction 1h, obtains sulfonic group lignin liquor; Be dissolved in water by 5g sodium formiate, preparation mass concentration is the aqueous solution of 10%, is 4 by the sulfuric acid adjust ph that mass concentration is 10%, at 30 DEG C, drips 5g epoxy chloropropane, and reaction 1h, obtains hydroxypropyl carboxylic acid sodium solution; Again by sulfonic group lignin liquor and the mixing of hydroxypropyl carboxylic acid sodium, be 8 by the NaOH aqueous solution adjust ph of 30%, temperature is react 0.5h at 80 DEG C; Then be incubated, dripping 5g mass concentration is that 30% otan carries out condensation end capping 2h, obtains liquid lignin-base dye dispersant after reaction terminates.
Fig. 1 is the infrared spectrogram of embodiment 1 product and wood pulp alkali xylogen.Can find out, compared with wood pulp alkali xylogen, embodiment 1 product is at 3420cm
-1neighbouring hydroxyl group absorption peak obviously weakens, and after modification is described, the phenolic hydroxyl group of product is reduced by end-blocking content; Wood pulp alkali xylogen is at 3039cm
-1(stretching vibration place of the c h bond of methylene radical, methyne) absorption peak is more weak, and embodiment 1 product is at 3039cm
-1place's absorption peak is comparatively strong, and the methyl in product is described, methylene radical increases, and the hydroxypropyl carboxylic acid sodium of long-chain branch is in phenyl ring grafting success; Compared with wood pulp alkali xylogen, embodiment 1 product is at 1647cm
-1there is stronger absorption at place, and this is the charateristic avsorption band of carbonyl, illustrates in embodiment 1 product and introduces more hydrophilic radical carboxyl; Embodiment 1 product is at 1188cm
-1and 1043cm
-1there is stronger absorption at place, and this is sulfonic characteristic peak, and the absorption peak of wood pulp alkali xylogen is more weak, and this illustrates in embodiment 1 products molecule and introduces more hydrophilic radical sulfonic group.
Fig. 2 is embodiment 1 product and wood pulp alkali xylogen
1h ?NMR spectrogram, can find out, wood pulp alkali xylogen is hydrocarbon polymer proton peak in 1.32ppm chemical shift place, and in embodiment 1 product, this peak, place is more weak, and after modification is described, side chain is replaced by grafting, has accessed the hydroxypropyl carboxylic acid sodium of long-chain branch.Wood pulp alkali xylogen is the methyl proton peak of m-methyl phenol at 1.80ppm place, and in embodiment 1 product, this peak, place is more weak, illustrates that in embodiment 1 product, this part phenolic hydroxyl group is closed, end-blocking success.Be the proton peak in phenolic hydroxyl group at 3.10 ~ 3.32ppm chemical shift region multiplet, embodiment 1 product signal intensity obviously weakens compared with wood pulp alkali xylogen, and after modification is described, phenolic hydroxyl group is closed obviously.3.51 ~ 3.62ppm chemical shift region Wei ?CH
2sO
3the proton peak of Na methylene, and as seen from Figure 2, the obvious enhancing compared with wood pulp alkali xylogen of embodiment 1 product signal intensity, side chain place sulfonation after modification is described, gets involved hydrophilic group sulfonic acid group.7.20 ~ 7.40ppm chemical shift region is the proton peak on phenyl ring, and wood pulp alkali xylogen compares clear signal wind, and embodiment 1 product signal is faint, illustrates that the H on phenyl ring is substituted, and phenyl ring there occurs and replace graft reaction and sulfonation reaction.
Embodiment 2
100g bamboo alkali lignin and sahio base xylogen blended solid powder are added to the water, stir the NaOH aqueous solution adjust ph to 11 that lower mass percent concentration is 30%, melt into mass concentration is the solution of 35%; Add 30g sodium m-aminobenzene sulfonate at being warming up to 90 DEG C, drip 3g Potassium Persulphate, reaction 2h, obtains sulfonic group lignin liquor; By 15g sodium formiate and sodium acetate mixed dissolution in water, preparation mass concentration is the aqueous solution of 20%, is 7 with the salt acid for adjusting pH value that mass concentration is 10%, at 50 DEG C, drips 20g epoxy chloropropane, and reaction 2h, obtains hydroxypropyl carboxylic acid sodium solution; Again by sulfonic group lignin liquor and the mixing of hydroxypropyl carboxylic acid sodium, be 10 by the KOH aqueous solution adjust ph of 30%, temperature is react 2h at 100 DEG C; Then be incubated, drip 15g mass concentration be 25% alpha-alcohol ketone and 3-hydroxy-2-butanone mixed solution carry out condensation end capping 4h, obtain liquid lignin-base dye dispersant after reaction terminates.
Embodiment 3
Be added to the water by 100g bagasse alkali-lignin pressed powder, stir the NaOH aqueous solution adjust ph to 10 that lower mass percent concentration is 30%, melt into mass concentration is the solution of 50%; Add 20g methylpropene sodium sulfonate at being warming up to 100 DEG C, drip 5g Sodium Persulfate, reaction 1.5h, obtains sulfonic group lignin liquor; Be dissolved in water by 20g sodium acrylate, preparation mass concentration is the aqueous solution of 40%, is 6 by the sulfuric acid adjust ph that mass concentration is 10%, at 40 DEG C, drips 15g epoxy chloropropane, and reaction 3h, obtains hydroxypropyl carboxylic acid sodium solution; Again by sulfonic group lignin liquor and the mixing of hydroxypropyl carboxylic acid sodium, be 12 by NaOH and the KOH aqueous solution adjust ph of 30%, temperature is react 2h at 90 DEG C; Then be incubated, drip 20g mass concentration be 30% hydroxy acetophenone carry out condensation end capping 3h, obtain liquid lignin-base dye dispersant after reaction terminates.
Embodiment 4
100g wood pulp alkali xylogen and bamboo alkali lignin pressed powder are added to the water, stir the NaOH aqueous solution adjust ph to 11 that lower mass percent concentration is 30%, melt into mass concentration is the solution of 40%; Add 20g sodium allyl sulfonate at being warming up to 80 DEG C, drip 2g Potassium Persulphate, reaction 1.5h, obtains sulfonic group lignin liquor; Be dissolved in water by 10g sodium oxalate, preparation mass concentration is the aqueous solution of 25%, is 5 by the sulfuric acid adjust ph that mass concentration is 10%, at 50 DEG C, drips 10g epoxy chloropropane, and reaction 3h, obtains hydroxypropyl carboxylic acid sodium solution; Again by sulfonic group lignin liquor and the mixing of hydroxypropyl carboxylic acid sodium, be 11 by the NaOH aqueous solution adjust ph of 30%, temperature is react 3h at 80 DEG C; Then be incubated, drip 10g mass concentration be 25% 2-hydroxy-2-methyl-5-hexanone carry out condensation end capping 2h, obtain liquid lignin-base dye dispersant after reaction terminates.
Embodiment 5
Be added to the water by 100g sahio base xylogen alkali lignin pressed powder, stir the NaOH aqueous solution adjust ph to 10 that lower mass percent concentration is 30%, melt into mass concentration is the solution of 10%; Add 15g chloroethyl sodium sulfonate at being warming up to 100 DEG C, drip 2g Sodium Persulfate, reaction 1.5h, obtains sulfonic group lignin liquor; Be dissolved in water by 5g Trisodium Citrate, preparation mass concentration is the aqueous solution of 40%, is 4 with the salt acid for adjusting pH value that mass concentration is 10%, at 50 DEG C, drips 20g epoxy chloropropane, and reaction 1h, obtains hydroxypropyl carboxylic acid sodium solution; Again by sulfonic group lignin liquor and the mixing of hydroxypropyl carboxylic acid sodium, be 9 by the KOH aqueous solution adjust ph of 30%, temperature is react 1h at 90 DEG C; Then be incubated, drip 15g mass concentration be 20% otan carry out condensation end capping 4h, obtain liquid lignin-base dye dispersant after reaction terminates.
Embodiment effect illustrates:
Table 1 is the molecular weight of embodiment of the present invention product, sulfonation degree and functional group content test data.
Table 1
Table 1 illustrates:
1. sodium lignosulfonate (wood pulp) is the product of raw material by acid polishing explained hereafter by Jilin stone Xian paper industry with timber;
2. the synthetic schemes of sulfonated wheat-strew lignin: take 100g wood pulp alkali xylogen, add 300 grams of water, stir after 30 minutes the pH value to 3 of the dilute sulphuric acid adjustment solution by mass concentration being 10%, filter, throw out adds the NaOH solution 400g that mass concentration is 2.5%, add 15 grams of hydrogen peroxide, 1 gram of ferrous sulfate, heat 60 DEG C of reactions after 60 minutes, be warming up to 85 DEG C, then adding 15 gram mass concentration is the formaldehyde solution of 37%, react 120 minutes, slowly add 10 grams of sodium sulphite anhydrous 99.3s, isothermal reaction 180 minutes;
3. naphthalenesulfonate formaldehyde condensation compound is commercial dyes dispersion agent product;
4. the mensuration of weight-average molecular weight adopts gel permeation chromatography, concrete test condition is as follows: get the lignosulfonic acid sodium sample that 3g mass concentration is 10%, after negatively charged ion, resin cation (R.C.) purifying, be mixed with the lignosulfonic acid sodium solution that mass concentration is 3 ‰, moving phase is 0.1mol/L NaNO
3, flow velocity 0.5mL/min take sodium polystyrene sulfonate as reference material;
5. sulfonation degree adopts automatic potentiometric titration to measure: sample is all through negatively charged ion, resin cation (R.C.) purifying;
6. the phenolic hydroxyl group in content of phenolic hydroxyl groups Folin-Ciocalteu reagent in titration sample, produce color reaction, by the colourity of ultraviolet spectrophotometer measured reaction, contrast obtains;
7. carboxyl-content adopts automatic potentiometric titration to measure: sample is all through negatively charged ion, resin cation (R.C.) purifying.
As seen from Table 1, the weight-average molecular weight of preparing product of the present invention reaches more than 10000Da, is obviously greater than the molecular weight of sodium lignosulfonate and sulfonated wheat-strew lignin.Sulfonation degree is all greater than 2.0mmol/g, and be greater than the 1.38mmol/g of sodium lignosulfonate, carboxyl-content is greater than 2.0mmol/g, is conducive to the water-soluble and dispersive ability improving dispersion agent.And the content of phenolic hydroxyl group is all less than 0.5mmol/g, far below sodium lignosulfonate and sulfonated lignin dispersion agent, this is conducive to reducing dispersion agent to the reduction of dyestuff and reduce contamination to fiber.
The test data being applied to dispersed dye performance that table 2 is embodiment of the present invention product.
Table 2
Table 2 illustrates:
(1) the dispersed dye system applied is C.I. Disperse Blue-79;
(2) preparation method of dye suspension system: according to quality than dispersion agent: dyestuff=1.5: 1 dispersion agent and the dyestuff adding synthesis respectively, then the ethylene glycol solvent of 5% is added, after add and be mixed with the system that mass concentration is 30, with ball mill ball milling 4h, obtain dye suspension system;
(3) particle diameter adopts the test of laser particle size particle shape analyser;
(4) test of suction filtration time is with reference to " GBT5541-2007, the mensuration double-layer filter paper filtration method of dispersed dye High Temperature Dispersion Stability ";
(5) test of contamination is with reference to " GBT2398-2003 ";
(6) reduction ratio test is by dye suspensions and pure dye, is the solution of mass concentration for 60mg/L of benchmark respectively, tests the coloured light colour strength of two solution, compare and obtain with ultraviolet spectrophotometer with acetone preparation with dyestuff;
(7) test of dye uptake is with reference to company standard: carry out upper dye with reference to " GBT2374-2007 ", tests the content of dyestuff in dye liquor before after upper dye respectively, compares and obtain dye uptake.
As seen from Table 2, the particle median size at normal temperatures of the dye dispersant system adopting product of the present invention to prepare is only 1.37 μm, is less than the particle diameter of other samples; The dye particle of the dyestuff-dispersant system after high temperature is less than 20 μm, and other samples are all more than 70 μm; After high temperature, the suction filtration time of double-layer filter paper method can be found out, the suction filtration time of the dye dispersant system adopting product of the present invention to prepare obviously is less than other products, and after the dispersiveness of embodiment product and high temperature can being described from particle diameter and suction filtration time, dispersion stabilization is better than other three kinds of dispersion agents;
The reduction ratio of preparing product of the present invention to dyestuff is only 9.63 ~ 11.35%, far below the destruction of other dispersion agents to dyestuff; Preparing product of the present invention is 4.5 grades to the contamination of fiber, close to having extremely low contamination naphthalenesulfonate formaldehyde condensation compound;
Dye uptake is dye dispersant dispersing property and the embodiment of over-all properties of reducing etc. to the destruction of dyestuff thereof.Dispersion agent dye uptake prepared by the present invention all reaches more than 80%, and application is obviously better than naphthalenesulfonate formaldehyde condensation compound conventional at present and sulfonated lignin dye dispersant and sodium lignosulfonate in the net effect of dyestuff.
Claims (8)
1. a preparation method for carboxyl sulfonic group xylogen dye dispersant, is characterized in that comprising the following steps:
(1) alkali lignin pressed powder is added to the water, be mixed with the aqueous solution that weight percent concentration is 20 ~ 50%, with alkaline conditioner adjust ph to 9 ~ 11, be warmed up to 75 ~ 100 DEG C, add containing sulfonic monomer, drip initiator, reaction 1 ~ 2h, obtains sulfonic group lignin liquor;
(2) be dissolved in water by carboxylic acid compound, be mixed with the solution that mass concentration is 10 ~ 40%, regulate pH to be 4 ~ 7, at temperature is 30 ~ 80 DEG C, add epoxy chloropropane with acid regulator, reaction 1 ~ 3h, obtains hydroxypropyl carboxylic acid cpd;
(3) by sulfonic group lignin liquor that step (1) is obtained by reacting, the hydroxypropyl carboxylic acid cpd be obtained by reacting with step (2) mixes, pH to 8 ~ 12 are regulated with alkaline conditioner, be heated to 80 ~ 100 DEG C, reaction 0.5 ~ 3h, drip mass concentration be 20 ~ 30% hydroxyl ketone thing carry out condensation end capping 2 ~ 6h, reaction terminate after obtain liquid carboxyl sulfonic group xylogen dye dispersant;
Above-mentioned raw materials is as follows with weight parts consumption:
Described alkali lignin is one or more the mixture in wood pulp alkali xylogen, bamboo alkali lignin, sahio base xylogen, bagasse alkali-lignin;
Described is one in sodium sulfanilate, sodium m-aminobenzene sulfonate, methylpropene sodium sulfonate, sodium allyl sulfonate, chloroethyl sodium sulfonate containing sulfonic monomer;
Described initiator is the one in ammonium persulphate, Sodium Persulfate and Potassium Persulphate;
Described carboxylic acid compound is one or both in sodium formiate, sodium acetate, sodium acrylate, sodium oxalate, Trisodium Citrate;
Described hydroxyl ketone thing is one or more of otan, alpha-alcohol ketone, 3-hydroxy-2-butanone, hydroxy acetophenone and 2-hydroxy-2-methyl-5-hexanone.
2. preparation method according to claim 1, is characterized in that: described step (2) temperature of reaction is 30 ~ 50 DEG C.
3. preparation method according to claim 1, is characterized in that: in described step (3), the polycondensation end capping time is 2 ~ 4h.
4. preparation method according to claim 1, is characterized in that: described acid regulator is sulfuric acid or hydrochloric acid.
5. preparation method according to claim 4, is characterized in that: the mass concentration of described sulfuric acid or hydrochloric acid is 10%.
6. preparation method according to claim 1, is characterized in that: described alkaline conditioner is the aqueous solution of sodium hydroxide or potassium hydroxide.
7. preparation method according to claim 6, is characterized in that: the aqueous solution mass concentration of described sodium hydroxide or potassium hydroxide is 30%.
8. a carboxyl sulfonic group lignin-base dye dispersant, it is characterized in that: it is by any one preparation of method described in claim 1-7, and its sulfonic content is greater than 2.00mmol/g, and carboxyl-content is greater than 2.0mmol/g, content of phenolic hydroxyl groups is less than 0.5mmol/g, and molecular weight is greater than 10000Da.
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| CN201310023758.2A CN103131020B (en) | 2013-01-22 | 2013-01-22 | Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof |
| PCT/CN2013/090093 WO2014114155A1 (en) | 2013-01-22 | 2013-12-20 | Lignin dye dispersant with carboxyl and sulfonic groups and preparation method therefor |
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Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131020B (en) * | 2013-01-22 | 2015-04-22 | 华南理工大学 | Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof |
| CN103397539B (en) * | 2013-07-10 | 2015-08-26 | 宁波市江北东丽化工助剂有限公司 | A kind of REACTIVE DYES promoter and preparation method thereof |
| CN103910890A (en) * | 2014-03-31 | 2014-07-09 | 济南圣泉集团股份有限公司 | Method for preparing sodium lignosulfonate and application of sodium lignosulfonate as a dye dispersant |
| CN104163925B (en) * | 2014-07-09 | 2016-10-05 | 华南理工大学 | A kind of Carboxylation alkali lignin sulfonate dye dispersant and preparation method thereof |
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| CN116356567A (en) * | 2023-04-21 | 2023-06-30 | 齐鲁工业大学(山东省科学院) | Preparation method of hydrophobic fabric, hydrophobic fabric and application |
| CN117105807B (en) * | 2023-06-20 | 2024-02-20 | 南京先进生物材料与过程装备研究院有限公司 | Lignin-based polyether amide surfactant and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001202A (en) * | 1975-10-17 | 1977-01-04 | Westvaco Corporation | Process for making sulfonated lignin surfactants |
| CN1137182C (en) * | 2000-12-27 | 2004-02-04 | 中国科学院广州化学研究所 | Process for preparing disperser by improving lignin |
| CN101147480B (en) * | 2007-09-13 | 2010-08-11 | 华南理工大学 | Modified lignosulfonate pesticide dispersing agent and its preparation method |
| CN101445522B (en) * | 2008-12-29 | 2011-03-23 | 邵国标 | Method for preparing modified kraft pulp sodium lignosulphonate |
| CN101575418B (en) * | 2009-06-19 | 2011-06-22 | 华南理工大学 | Lignin-based high-efficiency water reducing agent with high sulfonation degree and high molecular weight and method for preparing same |
| CN102134404B (en) * | 2011-01-11 | 2013-05-08 | 福州大学 | Modified lignin dispersant of disperse dye and preparation process thereof |
| CN102174273B (en) * | 2011-03-08 | 2013-07-10 | 延边石岘白麓纸业股份有限公司 | Method for preparing lignin sulfonate dye dispersant |
| CN102294199B (en) * | 2011-05-16 | 2013-10-30 | 福州大学 | Lignosulfonate grafted copolymer dispersant, preparation technology thereof, and application thereof |
| CN102321224B (en) * | 2011-06-27 | 2012-09-05 | 华南理工大学 | Modified alkali lignin ceramic grind-aid dispersing agent and preparation method thereof |
| CN102718962A (en) * | 2012-06-27 | 2012-10-10 | 淄博德信联邦化学工业有限公司 | Segmented polyether compound modified lignin and preparation method thereof |
| CN103131020B (en) * | 2013-01-22 | 2015-04-22 | 华南理工大学 | Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof |
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