CN103131020A - 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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- 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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- 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.Be take alkaline process papermaking byproduct alkali lignin as raw material specifically, prepare a kind of Lignins dye dispersant, this dye dispersant is applicable to the dispersion of the water-soluble dyes such as the insoluble dyes such as dispersed dye and reactive dyestuffs.
Background technology
Dye dispersant can reduce the dye granule particle diameter in the insoluble dyes attrition process processes such as dispersed dye, make dyestuff stable, be evenly dispersed in water; Dye dispersant also can stop the water-soluble dyes such as reactive dyestuffs to be assembled in water, forms comparatively even, stable dispersion liquid, so dye dispersant plays keying action in the processing of commercial dye and use procedure.
At present, the kind of dye dispersant commonly used has anionic and non-ionic type both at home and abroad.Anionic dispersing agents kind commonly used 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 relatively poor, and raw material sources are limited, the problem that toxicity is higher, especially the petrochemical industry resource 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, and as the acrylic acid graft copolymer dispersion agent, but cost is higher, and large-scale production and application also have the difficulty of a bit.Nonionogenic tenside commonly used has polyethylene glycol type and polyvalent alcohol type etc.This class dispersion agent can double as emulsifying agent etc., but more expensive.(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, has received increasing concern in recent years.
Xylogen is that occurring in nature content is only second to cellulosic second largest biomass resource, and simultaneously xylogen is the byproduct of paper industry, surpass at present 95% xylogen still with " black liquor " form directly enter rivers or concentrated after burn, seldom be utilized effectively.Development and utilization to xylogen has huge economic benefit and social benefit, and one of its main application is to be used as dye dispersant.The characteristics such as, source in extensive range due to the Lignins application of dispersant is abundant, with low cost and nontoxic are compared with similar petrochemicals, have 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 called again black liquid; What obtain with the sulfurous method boiling is sulfonated lignin.Along with acid polishing produces a large amount of spent acid, waste water, process the cost of waste water high and seriously polluted environment is caused very big injury, therefore acid polishing abandoned gradually, and change into take alkaline process as main, now, China's pulp industry is take alkaline process as main, also produced thus the black liquor of pulp making by product that contains in a large number alkali lignin, alkali lignin accounts for more than 90% of industrial lignin, but alkali lignin only is dissolved in strong alkali solution, the relatively poor water-soluble serious application that limits alkali lignin is often drained or is burned, contaminate environment and waste resource.The alkali lignin that reclaims in the black liquid has important using value and Significance for Environment as raw material prepares the xylogen dye dispersant.
The sulfonated wheat-strew lignin dye dispersant dyestuff is had good dispersing property but exist High Temperature Dispersion Stability can be poor, the reductibility of azo dyes is large, to problems such as the contamination of fiber are comparatively serious.
The general sulfonation reaction that adopts is prepared into the sulfonated lignin dispersion agent at present, and method of sulfonating is mainly normal pressure sulfomethylation method, High Temperature High Pressure sulfonation method, oxidation sulfonation method.Studies show that, sulfonation degree is higher, dispersion agent is stronger to the adsorptive power of dye molecule, the electrically charged increase of dye granule, the electrostatic repulsion between dyestuff increases, and makes dispersion liquid more stable, but because alkali lignin is the net macromolecular structure, shielding effect is apparent in view, and the sulfonation degree of the sulfonated lignin dispersion agent of present existing technology preparation is lower, and hydrophilic radical is less.In addition, present sulfonation reaction adopts S-WAT as sulphonating agent mostly, prepared that the 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 simultaneously the contamination to fiber.
When Lignin Dispersants dyes on to dyestuff attrition process and dye liquor high temperature, due to phenolic hydroxyl group in lignin structure with catechol group is oxidized makes it become quinonoid structure, make when self darkening, they also can interact with azoic dyestuff, dyestuff is reduced, destroy azo structure, cause dyestuff eclipsed.For solving the reduction problem of Lignin Dispersants to dyestuff, be mainly the content that reduces its phenolic hydroxyl group, as adopt epoxychloropropane modified method can effectively improve to a certain extent the contamination performance of Lignin Dispersants and the reductibility of azo dyes.Utilize epoxy chloropropane to carry out end capping to the phenolic hydroxyl group of sulfonated lignin as US Patent No. 4001202, reduce hydroxy radical content, reduce its contamination and reductibility, but its dispersing property and naphthalene are dispersion agent to be compared and still have a certain distance; US Patent No. 5989299 adopts trolamine, diethylamine uses by the dispersion agent of ion exchange reaction modified sodium lignosulfonate as the azoic dyestuff system, utilize the amine ion to suppress the reduction of azoic dyestuff in the azoic dyestuff system, thereby reduce the eclipsed of azoic dyestuff; US Patent No. 4444562 has been announced by adding intercalating agent (EDTA) to solve sulfonated lignin azo dyes reduction problem.
The lower-molecular-weight component of xylogen is also to cause one of important factor to the fiber contamination.The component of removing lower molecular weight in dispersion agent can reduce to fabric contamination, improve that it is dispersed and improve thermostability.Chinese patent CN87102691A after removing small molecules and impurity, prepares the xylogen dye dispersant with filtering through 80～100 mesh sieves after the sulfonation of non-wood plant alkali lignin.The Lignins dispersion agent of US Patent No. 1177617 preparation is to adopt ultrafiltration process to make after lower than 3000 composition except molecular weight in desulfonate or sulfomethylation xylogen, and its dispersing property is significantly improved." chemistry of forest product with industry " the 4th phase in 2003 has been announced the preparation method that modified wood vitriol xylogen prepares dye dispersant, get xylogen that middle recovery obtains as raw material take sulphite or alkaline process process, adopt acid out precipitator method purifying lignin, then under High Temperature High Pressure after sulphite sulfonation or sulphite-formaldehyde sulfomethylation, with epoxy chloropropane, the part phenolic hydroxyl group is sealed again, make simultaneously between lignin molecule crosslinkedly, obtain the modified lignin resin dye dispersant.
The molecular weight of Lignin Dispersants is larger, and the adsorptive power on the dyestuff discrete particles is stronger, under comparatively high temps, also is difficult for from the particle surface desorb and gets off, thereby kept thermostability and the dispersiveness of dye dispersion system.The compound (phenol, naphthols, benzylalcohol etc.) that Chinese patent CN102174273A announces sodium lignosulfonate, formaldehyde and contains hydroxyl carries out condensation reaction, obtains lignin sulfonate dye dispersant; US Patent No. 2680113, US4534771 alkali lignin sulfonation perhaps add formaldehyde to carry out aldol reaction after sulfonation, improve the lignin molecule amount.Adopting physical partition method to remove the small molecules xylogen prepares in the patent of xylogen dye dispersant, running cost is high, and the small molecules xylogen is not used and causes the waste of resource, existing technology is just for solving the single performances such as xylogen dye dispersant dispersiveness, reducing property simultaneously, sulfonation degree and molecular weight that prepared sulfonated lignin disperses are lower, still contain more phenolic hydroxyl group, at the High Temperature Dispersion Stability energy, still await further raising to the reducing property of dyestuff with to the aspect of performances such as contamination of fiber.
Summary of the invention
The carboxyl sulfonic group xylogen dye dispersant that the objective of the invention is a kind of excellent property poor for existing sulfonated lignin dye dispersant high temperature dispersibility, that the reductibility problem of the contamination of fiber and azo dyes is developed, this dispersion agent has good dispersing property to dyestuff, contamination to fiber is low, the characteristics that the reductibility of azo dyes is lower, and widen the recycling approach of black liquid.
The present invention also aims to provide the byproduct that utilizes paper-making pulping to prepare the method for xylogen dye dispersant.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of carboxyl sulfonic group xylogen dye dispersant comprises the following steps:
(1) the alkali lignin pressed powder is added to the water, is mixed with weight percent concentration and is 20～50% the aqueous solution, regulate pH value to 9～11 with alkaline conditioner, be warmed up to 75～100 ℃, add to contain sulfonic monomer, drip initiator, reaction 1～2h obtains the sulfonic group lignin liquor;
(2) carboxylic acid compound is dissolved in water, is mixed with mass concentration and is 10～40% solution, regulating pH with acid regulator is 4～7, is under 30～80 ℃ in temperature, adds epoxy chloropropane, and reaction 1～3h obtains the hydroxypropyl carboxylic acid cpd;
(3) the sulfonic group lignin liquor that step (1) reaction is obtained, the hydroxypropyl carboxylic acid cpd that obtains with step (2) reaction mixes, regulate pH to 8～12 with alkaline conditioner, be heated to 80～100 ℃, reaction 0.5～3h, drip mass concentration and be 20～30% hydroxyl ketone thing and carry out condensation end capping 2～6h, reaction obtains liquid carboxyl sulfonic group xylogen dye dispersant after finishing;
Above-mentioned raw materials is as follows in the parts by weight consumption:
Described alkali lignin is one or more the mixture in wood pulp alkali xylogen, bamboo alkali lignin, sahio base xylogen, bagasse alkali-lignin;
It is described that to contain sulfonic monomer be a kind of in sodium sulfanilate, m-sulfanilic acid sodium, methylpropene sodium sulfonate, sodium allyl sulfonate, chloroethyl sodium sulfonate;
Described initiator is a kind of 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 further realizing the object of the invention, described step (2) temperature of reaction is preferably 30～50 ℃.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 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 has following advantage and effect:
The carboxyl sulfonic group lignin-base dye dispersant that contains of the present invention's preparation has following characteristics:
1) the lignin-base dye dispersant of the technology of the present invention preparation access carboxyl and sulfonic group hydrophilic functional group on the hydrophobic framework phenylpropyl alcohol alkyl structure unit of alkali lignin, can make dispersion agent phenyl ring and dye molecule produce π-π interacts, hydrophilic group is soluble in water, adsorb on dye granule, thereby produce larger effective Coulomb repulsion and sterically hindered effect, therefore have good 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, and the phenolic hydroxyl group in lignin structure is had certain sealing process; Adopt hydroxyl ketone thing to carry out the polycondensation end capping to alkali lignin, not only improve the molecular weight of dispersion agent, seal again the phenols 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 the carboxyl sulfonic group xylogen dye dispersant of the present invention's preparation 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 simultaneously the carboxyl of certain content, have higher negative charge density, can significantly improve dyestuff grinding efficiency, improve the dispersion effect to insoluble dispersed dye.
4) the technology of the present invention adopts the 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 is lower than less than 0.5mmol/g, significantly reduces the reduction of azo dyes and to the contamination of fiber.
5) existing dye dispersant such as naphthalenesulfonate formaldehyde condensation compound main raw material are petroleum chemicalss, and certain toxicity is arranged, and cost is higher.Main raw material alkali lignin in the technology of the present invention comes from the alkaline process byproduct, belongs to green renewable resources, and raw material sources are abundant, environment-protecting asepsis, are also the recyclings to waste, and energy-saving and emission-reduction, protection of the environment are significant.Production technique of the present invention below 100 ℃, is that dispersion agent is compared with naphthalene under normal pressure in addition, and synthesis technique is simple, production cost is low.
6) product of the present invention's preparation is compared with the naphthalene sulfonic dipersant, structurally except containing sulfonic group, has also increased carboxyl, and molecular weight is larger simultaneously, and is more excellent than naphthalene sulfonic dipersant to the High Temperature Disperse performance of dyestuff.
Description of drawings
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
1The H-NMR spectrogram.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiments and the drawings, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
100g wood pulp alkali xylogen pressed powder is added to the water, and is 30% NaOH aqueous solution adjusting pH value to 9 with mass percent concentration under stirring, and the melt into mass concentration is 20% solution; Be warming up to and add the 10g sodium sulfanilate under 75 ℃, drip the 1g ammonium persulphate, reaction 1h obtains the sulfonic group lignin liquor; The 5g sodium formiate is dissolved in water, and the preparation mass concentration is 10% the aqueous solution, is that 10% sulphur acid for adjusting pH value is 4 with mass concentration, under 30 ℃, drips the 5g epoxy chloropropane, reacts 1h, obtains hydroxypropyl carboxylic acid sodium solution; Sulfonic group lignin liquor and hydroxypropyl carboxylic acid sodium are mixed, it is 8 that the NaOH aqueous solution with 30% is regulated the pH value again, and temperature is to react 0.5h under 80 ℃; Then insulation, dripping the 5g mass concentration is that 30% otan carries out condensation end capping 2h, reaction obtains liquid lignin-base dye dispersant after finishing.
Fig. 1 is the infrared spectrogram of embodiment 1 product and wood pulp alkali xylogen.Can find out, compare with the wood pulp alkali xylogen, embodiment 1 product is at 3420cm
-1Near the hydroxyl absorption peak obviously weaken, illustrate modification afterwards the phenolic hydroxyl group of product reduced by end-blocking content; The wood pulp alkali xylogen is at 3039cm
-1(stretching vibration place of the c h bond of methylene radical, methyne) absorption peak a little less than, embodiment 1 product is at 3039cm
-1Place's absorption peak is stronger, 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; Compare with the wood pulp alkali xylogen, embodiment 1 product is at 1647cm
-1There is stronger absorption at the place, and this is the charateristic avsorption band of carbonyl, and the more hydrophilic radical carboxyl of introducing in embodiment 1 product is described; Embodiment 1 product is at 1188cm
-1And 1043cm
-1There is stronger absorption at the place, and this is sulfonic characteristic peak, the absorption peak of wood pulp alkali xylogen a little less than, has introduced more hydrophilic radical sulfonic group in this explanation embodiment 1 products molecule.
Fig. 2 is embodiment 1 product and wood pulp alkali xylogen
1H ?the NMR spectrogram, can find out, the wood pulp alkali xylogen is the hydrocarbon polymer proton peak in 1.32ppm chemical shift place, in embodiment 1 product should the place peak a little less than, after modification was described, side chain was replaced by grafting, had accessed the hydroxypropyl carboxylic acid sodium of long-chain branch.The wood pulp alkali xylogen is the methyl proton peak of m-methyl phenol at the 1.80ppm place, should peak, place in embodiment 1 product a little less than, illustrate that in embodiment 1 product, this part phenolic hydroxyl group is closed, end-blocking successfully.Be the proton peak in phenolic hydroxyl group at 3.10～3.32ppm chemical shift region multiple peak, embodiment 1 product signal intensity is compared obviously with the wood pulp alkali xylogen and is weakened, modification is described after phenolic hydroxyl group be closed obviously.3.51～3.62ppm chemical shift zone Wei ?CH
2SO
3The proton peak of methylene radical in Na, and as seen from Figure 2, embodiment 1 product signal intensity is compared obvious enhancing with the wood pulp alkali xylogen, and modification side chain place's sulfonation afterwards is described, gets involved the hydrophilic group sulfonic acid group.7.20～7.40ppm chemical shift zone is the proton peak on phenyl ring, the wood pulp alkali xylogen is compared clear signal wind, and embodiment 1 product signal is faint, illustrates that the H on phenyl ring is substituted, and replacement graft reaction and sulfonation reaction have occured on phenyl ring.
100g bamboo alkali lignin and sahio base xylogen blended solid powder are added to the water, and are 30% NaOH aqueous solution adjusting pH value to 11 with mass percent concentration under stirring, and the melt into mass concentration is 35% solution; Be warming up to and add 30g m-sulfanilic acid sodium under 90 ℃, drip the 3g Potassium Persulphate, reaction 2h obtains the sulfonic group lignin liquor; In water, the preparation mass concentration is 20% the aqueous solution with 15g sodium formiate and sodium acetate mixed dissolution, is that 10% salt acid for adjusting pH value is 7 with mass concentration, under 50 ℃, drips the 20g epoxy chloropropane, reacts 2h, obtains hydroxypropyl carboxylic acid sodium solution; Sulfonic group lignin liquor and hydroxypropyl carboxylic acid sodium are mixed, it is 10 that the KOH aqueous solution with 30% is regulated the pH value again, and temperature is to react 2h under 100 ℃; Then insulation drips the 15g mass concentration and is 25% alpha-alcohol ketone and 3-hydroxy-2-butanone mixed solution and carries out condensation end capping 4h, and reaction obtains liquid lignin-base dye dispersant after finishing.
100g bagasse alkali-lignin pressed powder is added to the water, and is 30% NaOH aqueous solution adjusting pH value to 10 with mass percent concentration under stirring, and the melt into mass concentration is 50% solution; Be warming up to and add the 20g methylpropene sodium sulfonate under 100 ℃, drip the 5g Sodium Persulfate, reaction 1.5h obtains the sulfonic group lignin liquor; The 20g sodium acrylate is dissolved in water, and the preparation mass concentration is 40% the aqueous solution, is that 10% sulphur acid for adjusting pH value is 6 with mass concentration, under 40 ℃, drips the 15g epoxy chloropropane, reacts 3h, obtains hydroxypropyl carboxylic acid sodium solution; Sulfonic group lignin liquor and hydroxypropyl carboxylic acid sodium are mixed, it is 12 that the NaOH with 30% and the KOH aqueous solution are regulated the pH value again, and temperature is to react 2h under 90 ℃; Then insulation drips the 20g mass concentration and is 30% hydroxy acetophenone and carries out condensation end capping 3h, and reaction obtains liquid lignin-base dye dispersant after finishing.
100g wood pulp alkali xylogen and bamboo alkali lignin pressed powder are added to the water, and are 30% NaOH aqueous solution adjusting pH value to 11 with mass percent concentration under stirring, and the melt into mass concentration is 40% solution; Be warming up to and add the 20g sodium allyl sulfonate under 80 ℃, drip the 2g Potassium Persulphate, reaction 1.5h obtains the sulfonic group lignin liquor; The 10g sodium oxalate is dissolved in water, and the preparation mass concentration is 25% the aqueous solution, is that 10% sulphur acid for adjusting pH value is 5 with mass concentration, under 50 ℃, drips the 10g epoxy chloropropane, reacts 3h, obtains hydroxypropyl carboxylic acid sodium solution; Sulfonic group lignin liquor and hydroxypropyl carboxylic acid sodium are mixed, it is 11 that the NaOH aqueous solution with 30% is regulated the pH value again, and temperature is to react 3h under 80 ℃; Then insulation drips the 10g mass concentration and is 25% 2-hydroxy-2-methyl-5-hexanone and carries out condensation end capping 2h, and reaction obtains liquid lignin-base dye dispersant after finishing.
100g sahio base xylogen alkali lignin pressed powder is added to the water, and is 30% NaOH aqueous solution adjusting pH value to 10 with mass percent concentration under stirring, and the melt into mass concentration is 10% solution; Be warming up to and add 15g chloroethyl sodium sulfonate under 100 ℃, drip the 2g Sodium Persulfate, reaction 1.5h obtains the sulfonic group lignin liquor; The 5g Trisodium Citrate is dissolved in water, and the preparation mass concentration is 40% the aqueous solution, is that 10% salt acid for adjusting pH value is 4 with mass concentration, under 50 ℃, drips the 20g epoxy chloropropane, reacts 1h, obtains hydroxypropyl carboxylic acid sodium solution; Sulfonic group lignin liquor and hydroxypropyl carboxylic acid sodium are mixed, it is 9 that the KOH aqueous solution with 30% is regulated the pH value again, and temperature is to react 1h under 90 ℃; Then insulation drips the 15g mass concentration and is 20% otan and carries out condensation end capping 4h, and reaction obtains liquid lignin-base dye dispersant after finishing.
The explanation of embodiment effect:
Table 1 is molecular weight, sulfonation degree and the functional group content test data of embodiment of the present invention product.
Table 1
Table 1 explanation:
Sodium lignosulfonate (wood pulp) be by Jilin stone Xian paper industry take timber as raw material by the product of acid polishing explained hereafter;
2. the synthetic schemes of sulfonated wheat-strew lignin: take 100g wood pulp alkali xylogen, add 300 gram water, stirring after 30 minutes with mass concentration is the pH value to 3 that 10% dilute sulphuric acid is adjusted solution, filter, it is 2.5% NaOH solution 400g that throw out adds mass concentration, add 15 gram hydrogen peroxide, 1 gram ferrous sulfate, heat 60 ℃ of reactions after 60 minutes, be warming up to 85 ℃, then adding 15 gram mass concentration is 37% formaldehyde solution, reacted 120 minutes, and slowly added 10 gram sodium sulphite anhydrous 99.3s, isothermal reaction 180 minutes;
3. naphthalenesulfonate formaldehyde condensation compound is commercially available dye dispersant product;
4. the mensuration of weight-average molecular weight adopts gel permeation chromatography, concrete test condition is as follows: get the 3g mass concentration and be 10% lignosulfonic acid sodium sample, after negatively charged ion, resin cation (R.C.) purifying, be mixed with mass concentration and be 3 ‰ lignosulfonic acid sodium solution, moving phase is 0.1mol/L NaNO
3, flow velocity 0.5mL/min is take sodium polystyrene sulfonate as reference material;
5. sulfonation degree is to adopt automatic potentiometric titration to measure: sample is all through negatively charged ion, resin cation (R.C.) purifying;
6. the phenolic hydroxyl group in the titration sample in content of phenolic hydroxyl groups Folin-Ciocalteu reagent, produce color reaction, and by the colourity of ultraviolet spectrophotometer measured reaction, contrast obtains;
7. carboxyl-content is to adopt automatic potentiometric titration to measure: sample is all through negatively charged ion, resin cation (R.C.) purifying.
As seen from Table 1, more than the weight-average molecular weight of preparing product of the present invention reaches 10000Da, obvious molecular weight greater than sodium lignosulfonate and sulfonated wheat-strew lignin.Sulfonation degree is all greater than 2.0mmol/g, and greater than the 1.38mmol/g of sodium lignosulfonate, carboxyl-content is conducive to improve the water-soluble and dispersive ability of dispersion agent greater than 2.0mmol/g.And the content of phenolic hydroxyl group is all less than 0.5mmol/g, and far below sodium lignosulfonate and sulfonated lignin dispersion agent, this is conducive to reduce dispersion agent to the reduction of dyestuff and reduces contamination to fiber.
Table 2 is applied to dispersed dye performance test data for embodiment of the present invention product.
Table 2
Table 2 explanation:
(1) applied dispersed dye system is the C.I. Disperse Blue-79;
(2) preparation method of dye suspension system: according to quality than dispersion agent: dyestuff=1.5: 1 adds respectively synthetic dispersion agent and dyestuff, then add 5% ethylene glycol solvent, after add that to be mixed with mass concentration be 30 system, with ball mill ball milling 4h, obtain the dye suspension system;
(3) particle diameter is to adopt the test of laser particle size particle shape analyser;
(4) test of suction filtration time is with reference to " GBT5541-2007, the double-deck filter paper filtering method of the mensuration of dispersed dye High Temperature Dispersion Stability ";
(5) test of contamination is with reference to " GBT2398-2003 ";
(6) the reduction ratio test is with dye suspensions and pure dye, and with the solution of the mass concentration of acetone preparation take dyestuff as benchmark as 60mg/L, with the coloured light colour strength of ultraviolet spectrophotometer test two solution, comparing obtains respectively;
(7) test of dye uptake is with reference to company standard: dye on carrying out with reference to " GBT2374-2007 ", dye respectively the content of dyestuff in rear front dye liquor in the test, comparing obtains dye uptake.
As seen from Table 2, adopting the particle median size at normal temperatures of the dye dispersant system of product preparation of the present invention is only 1.37 μ m, less than the particle diameter of other samples; The dye particle of the dyestuff-dispersant system after high temperature is less than 20 μ m, and other samples are all more than 70 μ m; After high temperature, the suction filtration time of double-deck filter paper method can be found out, adopt the suction filtration time of the dye dispersant system of product of the present invention preparation obviously to be less than other products, from particle diameter and suction filtration time, the dispersiveness of embodiment product and high temperature can be described after dispersion stabilization better than other three kinds of dispersion agents;
Preparing product of the present invention is only 9.63～11.35% to the reduction ratio of dyestuff, 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, approaches to have extremely low contamination naphthalenesulfonate formaldehyde condensation compound;
Dye uptake is dye dispersant dispersing property and to the embodiment of the over-all propertieies such as destruction reduction of dyestuff.The dispersion agent dye uptake of the present invention's preparation all reaches more than 80%, and application obviously is better than naphthalenesulfonate formaldehyde condensation compound and sulfonated lignin dye dispersant and sodium lignosulfonate commonly used at present in the net effect of dyestuff.
Claims (8)
1. the preparation method of a carboxyl sulfonic group xylogen dye dispersant is characterized in that comprising the following steps:
(1) the alkali lignin pressed powder is added to the water, is mixed with weight percent concentration and is 20～50% the aqueous solution, regulate pH value to 9～11 with alkaline conditioner, be warmed up to 75～100 ℃, add to contain sulfonic monomer, drip initiator, reaction 1～2h obtains the sulfonic group lignin liquor;
(2) carboxylic acid compound is dissolved in water, is mixed with mass concentration and is 10～40% solution, regulating pH with acid regulator is 4～7, is under 30～80 ℃ in temperature, adds epoxy chloropropane, and reaction 1～3h obtains the hydroxypropyl carboxylic acid cpd;
(3) the sulfonic group lignin liquor that step (1) reaction is obtained, the hydroxypropyl carboxylic acid cpd that obtains with step (2) reaction mixes, regulate pH to 8～12 with alkaline conditioner, be heated to 80～100 ℃, reaction 0.5～3h, drip mass concentration and be 20～30% hydroxyl ketone thing and carry out condensation end capping 2～6h, reaction obtains liquid carboxyl sulfonic group xylogen dye dispersant after finishing;
Above-mentioned raw materials is as follows in the parts by weight consumption:
Described alkali lignin is one or more the mixture in wood pulp alkali xylogen, bamboo alkali lignin, sahio base xylogen, bagasse alkali-lignin;
It is described that to contain sulfonic monomer be a kind of in sodium sulfanilate, m-sulfanilic acid sodium, methylpropene sodium sulfonate, sodium allyl sulfonate, chloroethyl sodium sulfonate;
Described initiator is a kind of 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, it is characterized in that: described step (2) temperature of reaction is 30～50 ℃.
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, it is characterized in that: described acid regulator is sulfuric acid or hydrochloric acid.
5. preparation method according to claim 1, it is characterized in that: the mass concentration of described sulfuric acid or hydrochloric acid is 10%.
6. preparation method according to claim 1, it is characterized in that: described alkaline conditioner is the aqueous solution of sodium hydroxide or potassium hydroxide.
7. preparation method according to claim 1, it is characterized in that: the aqueous solution mass concentration of described sodium hydroxide or potassium hydroxide is 30%.
8. carboxyl sulfonic group lignin-base dye dispersant, it is characterized in that: it is by any preparation of the described method of 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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