CN102134404A - Modified lignin dispersant of disperse dye and preparation process thereof - Google Patents

Abstract

The invention relates to a modified lignin dispersant of a disperse dye and a preparation process thereof. The dispersant of the disperse dye comprises the following raw materials in parts by mass: 45.0-74.0 parts of pulping black liquid, 0.5-4.0 parts of oxidant, 3.0-8.0 parts of aldehydes, 0.5-5.4 parts of anion etherifying agent, 2.6-20.0 parts of amines, 8.0-18.0 parts of sulfonating agent and 10.0-30.0 parts of water. In the preparation process, black liquid produced in pulping industry is directly utilized to prepare the dispersant of the disperse dye, wherein the thermal stability of the dispersant at the temperatures of 130 DEG C and 150 DEG C is above level 4, the staining property of chinlon, terylene and cotton is above level 4, and the dispersion force of the dispersant is greater than 95%; on the basis that the cost of the product is greatly reduced, performances such as the dispersion force, the thermal stability and the like of the product are improved; the 'three wastes' are not discharged in the whole production process; and the high-value utilization of lignin is realized; and therefore, the preparation process is a clean and environment-friendly process.

Description

A kind of modified lignin disperse dye dispersant and its preparation process

technical field

The invention belongs to the field of fine chemicals, and in particular relates to a modified lignin disperse dye dispersant and a preparation process thereof.

Background technique

In today's world, the reserves of oil and natural gas resources are limited, and their research, development and utilization have an increasingly serious impact on the earth's ecological environment, which has prompted the vigorous development of polymer materials that use natural resources as raw materials. Lignin is one of the most abundant and renewable natural polymer resources in nature. Land plants in the world can produce 50 billion tons of lignin every year, of which 50 million tons of industrial lignin are produced in the cooking waste liquid of the pulp and paper industry. At present, my country's pulping and papermaking industry is dominated by alkaline and kraft pulping. Some large pulping and papermaking enterprises can use alkali recovery technology to burn pulping black liquor and recover alkali liquor to eliminate the pollution of pulping black liquor , but this method will cause a huge waste of lignin resources. Therefore, lignin has not been well utilized so far, and only about 6% of lignin in my country has been utilized. How to effectively utilize lignin, a renewable resource, and increase its added value has become the starting point for researchers.

Disperse dyes are a class of non-ionic dyes with low water solubility. It was first used for the dyeing of acetate fiber, known as acetate dye. With the development of synthetic fibers, nylon and polyester have appeared one after another, which put forward new requirements for dyes. It is estimated that 60,000 to 100,000 tons of dispersants are used in post-processing of dyestuffs in China alone. The quality of the dispersant directly affects the quality of the dye and the entire dyeing process, therefore, the dispersant is extremely important. At present, there are several types of dye dispersants commonly used in the domestic and foreign markets: (1) naphthalenesulfonic acid formaldehyde condensate dispersant; (2) polycarboxylic acid dispersant; (3) modified lignin dispersant agent.

Among them, the heat-resistant stability of naphthalenesulfonic acid formaldehyde condensate dispersant is not high, generally only 120~130 ℃, and its raw material (methylnaphthalene) is far from meeting the needs of production, and the product cost is high, which affects the performance of naphthalenesulfonate. The price of the acid-formaldehyde condensate dispersant product is not conducive to the promotion and application of the product in the analysis of dyes. However, polycarboxylic acid-based dispersants have harsh reaction conditions, complex processes, and high industrialization costs. At the same time, the monomer coverage of the existing active polymerization technology is narrow, mainly monomers such as styrene and (meth)acrylates. less designability. The main advantages of using modified lignin as a dye dispersant are (1) wide source of raw materials, easy to obtain, and low cost; (2) good compatibility with many types of dye systems and excellent dispersion performance . But at the same time, there are still some difficult problems to solve when lignin is used as a dye dispersant, such as lignin's dyeing of fibers and its heat resistance stability. The overcoming of these difficulties has become a hot research topic of domestic and foreign experts.

In recent years, the research on modified lignin dye dispersants mainly focuses on the appropriate chemical modification of lignin to improve its performance, especially heat resistance. Wang K C uses polyethylene glycol epoxy ethers EO-1, EO-2, and EO-3 as dispersing aids, which can be used in combination with lignosulfonate. However, compounding cannot change the hydrophilic and lipophilic groups and their surface activity in lignosulfonate molecules, and the price is relatively high. Therefore, chemical modification of lignosulfonate can prepare highly efficient modified lignosulfonate dispersant (US 6066183). Dilling P uses sodium dithionite to pretreat lignin, and then reacts sodium sulfite and aldehyde with modified lignin to improve the heat resistance of lignin (US 4338091). Wei Handao et al. used electro-oxidation and sulfomethylation methods combining physics and chemistry to provide a method for preparing dispersants by modifying lignin with mild reaction conditions, no pollution, and excellent product dispersibility (ZL 00131005.4).

Therefore, if lignin is used as raw material, a modified lignin vat dye dispersant with a certain degree of sulfonation is developed through chemical modification, which will not only greatly reduce the price of vat dye dispersant products, but also facilitate the dispersion of modified lignin vat dyes. The popularization and application of lignin will further broaden the application range of lignin and increase its added value. At the same time, it will also increase the enthusiasm of enterprises to comprehensively utilize lignin and solve the pollution of pulp and paper black liquor, and promote the sustainable and healthy development of my country's pulp and paper industry. .

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art, increase the added value of lignin and solve the problems of poor heat resistance and high cost of traditional disperse dye dispersants, and provide a modified lignin disperse dye dispersant and its preparation process . This process directly uses the black liquor produced in the pulping industry to prepare a dispersant for disperse dyes, so as to reduce or eliminate the pollution to the environment during production and use, and improves the dispersion of the product on the basis of greatly reducing the product cost. strength and thermal stability.

The present invention is implemented through the following technical solutions:

The raw material composition and mass parts thereof of a kind of modified lignin disperse dye dispersant are:

Pulping black liquor: 45.0 to 74.0 parts

Oxidizing agent: 0.5 to 4.0 parts

Aldehyde compounds: 3.0 to 8.0 parts

Anionic etherification agent: 0.5 to 5.4 parts

Amine compounds: 2.6 to 20.0 parts

Sulfonating agent: 8.0 to 18.0 parts

Water: 10.0 to 30.0 parts.

The relative molecular weight of the dispersant is 3000-41000, and it is dark brown viscous liquid or brown powder.

When the mass concentration of the dispersant aqueous solution is 1%, the pH is 7.5-10.5.

The heat resistance stability of the dispersant at 130°C and 150°C is above grade 4, and the staining property of nylon, polyester and cotton is above grade 4,

Dispersion power greater than 95%.

The specific steps of the preparation process of the modified lignin disperse dye dispersant are:

React pulping black liquor and oxidant at a temperature of 40-95°C for 10-30 minutes, add aldehyde compounds, continue to react for 0.5-2 hours, then raise the temperature to 90-160°C, then add anion etherifying agent to react with amine compounds After 0.5-1.5 hours, add the mixture of sulfonating agent and water, and react for 0.5-2 hours to prepare the dispersant. The prepared dispersant is a dark brown liquid, and the tan solid powder can be obtained after spray drying; Preparation is carried out under normal pressure.

The preparation method of the described pulping black liquor is: select one or more of bamboo, bagasse, rice straw, wheat straw, imperial bamboo grass, Achnatherum splendens, Qu Liu, oak, poplar, reed, eucalyptus, birch, masson pine The first is to prepare pulping black liquor by alkali method or sulfate method. The solid content of the black liquor is 8% to 75%, the lignin content is 9% to 45%, and the density is 1.13 to 1.51 g/ml.

The oxidant is one or more of potassium permanganate, hydrogen peroxide, potassium ferrate, sodium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, and sodium hypochlorite.

The aldehyde compound is one or more of formaldehyde, acetaldehyde, glutaraldehyde, acrolein, succinaldehyde, melamine formaldehyde, paraformaldehyde and paraformaldehyde.

The anionic etherifying agent is one or more of ethylene oxide, propylene oxide, epichlorohydrin, hexadecane bromide, and monochloroacetic acid.

The amine compound is one or more of dimethylamine, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, formamide, acetamide, diethylenetriamine, and phenylenediamine.

The sulfonating agent is one or more of sodium sulfite, sodium bisulfite, chlorosulfonic acid, sodium pyrosulfite, sodium isethionate, ammonium sulfite, and sulfamic acid.

The advantages of the present invention are:

1) The present invention mainly uses lignin, a by-product in the pulping industry, as a raw material, so that the developed product has the characteristics of low cost.

2) The present invention directly modifies the pulping black liquor after concentration, and does not need to recover lignin through acidification treatment before modification. The whole production process does not discharge "three wastes" (exhaust gas, waste water, waste residue), and solves the problem of pulping and paper mills. Therefore, this preparation process is a clean and environment-friendly process. While reducing the production cost of the product, it also improves the dispersibility and heat resistance stability of the product. At present, there are no literature reports at home and abroad.

3) The present invention uses suitable oxidizing agents, etherifying agents and amine compounds to modify lignin to improve the heat resistance stability of the dispersant. The heat resistance stability of the product at 150°C after being combined with vat dyes is grade four above.

4) The production process of the present invention is simple, the production raw materials are easy to obtain, the production cycle is short, the reaction is mild, and the required equipment is conventional equipment, which is convenient for existing chemical plants to start production.

Description of drawings

Figure 1 is the application effect of disperse dye dispersant on the heat resistance stability of different disperse dyes at 150°C;

Figure 2 shows the application effect of disperse dye dispersants on the thermal stability of disperse dyes at different temperatures.

Detailed ways

The raw material composition and mass parts thereof of a kind of modified lignin disperse dye dispersant are:

Pulping black liquor: 45.0 to 74.0 parts

Oxidizing agent: 0.5 to 4.0 parts

Aldehyde compounds: 3.0 to 8.0 parts

Anionic etherification agent: 0.5 to 5.4 parts

Amine compounds: 2.6 to 20.0 parts

Sulfonating agent: 8.0 to 18.0 parts

Water: 10.0 to 30.0 parts.

The specific steps of the preparation process of the modified lignin disperse dye dispersant are:

React pulping black liquor and oxidant at a temperature of 40-95°C for 10-30 minutes, add aldehyde compounds, continue to react for 0.5-2 hours, then raise the temperature to 90-160°C, then add anion etherifying agent to react with amine compounds After 0.5-1.5 hours, add the mixture of sulfonating agent and water, and react for 0.5-2 hours to prepare the dispersant. The prepared dispersant is a dark brown liquid, and the tan solid powder can be obtained after spray drying; Preparation is carried out under normal pressure.

The preparation method of the described pulping black liquor is: select one or more of bamboo, bagasse, rice straw, wheat straw, imperial bamboo grass, Achnatherum splendens, Qu Liu, oak, poplar, reed, eucalyptus, birch, masson pine The first is to prepare pulping black liquor by alkali method or sulfate method. The solid content of the black liquor is 8% to 75%, the lignin content is 9% to 45%, and the density is 1.13 to 1.51 g/ml.

The oxidant is one or more of potassium permanganate, hydrogen peroxide, potassium ferrate, sodium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, and sodium hypochlorite.

The aldehyde compound is one or more of formaldehyde, acetaldehyde, glutaraldehyde, acrolein, succinaldehyde, melamine formaldehyde, paraformaldehyde and paraformaldehyde.

The anionic etherifying agent is one or more of ethylene oxide, propylene oxide, epichlorohydrin, hexadecane bromide, and monochloroacetic acid.

The amine compound is one or more of dimethylamine, ethylenediamine, ethanolamine, diethanolamine, triethanolamine, formamide, acetamide, diethylenetriamine, and phenylenediamine.

The sulfonating agent is one or more of sodium sulfite, sodium bisulfite, chlorosulfonic acid, sodium pyrosulfite, sodium isethionate, ammonium sulfite, and sulfamic acid.

Example 1

1) Raw materials and formulations of this example (unit - kilogram):

Alkaline bamboo pulping black liquor (mass fraction 75%): 450.0 kg

Hydrogen peroxide: 5.0 kg

Formaldehyde: 60.0 kg

Ethylene oxide: 18.0 kg

Dimethylamine: 78.0 kg

Sodium sulfite: 180.0 kg

Water: 209.0 kg

2) Process steps and process parameters

The preparation of the present invention is carried out under normal pressure:

First preheat the reactor to 40°C, add 450.0 kg of pulping black liquor with a mass fraction of 45% calculated, 5.0 kg of hydrogen peroxide, react for 10 min, add 60.0 kg of formaldehyde, continue the reaction for 1 h and then raise the temperature to 90 ℃, then add 18.0 kg of ethylene oxide, 78.0 kg of dimethylamine, react for 0.5 h, finally add a mixture of 180.0 kg of sodium sulfite and 209.0 kg of water, react for 1.5 h, cool down and discharge, the prepared product is dark brown The liquid is spray-dried to obtain a tan solid powder, using a QZP-500 pressure spray dryer: the inlet air temperature of the spray tower is 230°C, and the outlet air temperature is 80°C. The molecular weight of the product is 17000.

Example 2

1) Raw materials and formulations of this example (unit - kilogram):

Alkali pulping black liquor (mixture of bamboo and bagasse, mass ratio 6:4, solid content of concentrated black liquor 8%): 740.0 kg

Potassium permanganate: 10.0 kg

Acetaldehyde: 30.0 kg

Propylene oxide: 10.0 kg

Ethylenediamine: 26.0 kg

Sodium metabisulfite: 80.0 kg

Water: 104.0 kg

2) Process steps and process parameters

The preparation of the present invention is carried out under normal pressure:

First preheat the reactor to 60°C, add 740.0 kg of pulping black liquor with a mass fraction of 40% that has been calculated, 10.0 kg of potassium permanganate, react for 10 min, add 30.0 kg of acetaldehyde, and continue the reaction for 0.5 h Raise the temperature to 100°C, then add 10.0 kg of ethylene oxide and 26.0 kg of ethylenediamine, react for 0.5 h, and finally add a mixture of 80.0 kg of sodium metabisulfite and 104.0 kg of water, react for 1.5 h, cool down and discharge, the prepared product It is a dark brown liquid, and after spray drying, a brown solid powder can be obtained. The LPG-150 spray dryer is used: the inlet air temperature of the spray tower is 280°C, and the outlet air temperature is 120°C. The molecular weight of the product is 9800.

Example 3

1) Raw materials and formulations of this example (unit - kilogram):

Alkali pulping black liquor (mixture of bamboo and rice straw, mass ratio 4:1, black liquor solid content 48%): 488.0 kg

Hydrogen peroxide: 20.0 kg

Potassium permanganate: 5.0 kg

Formaldehyde: 60.0 kg

Acrolein: 20.0 kg

Monochloroacetic acid: 14.0 kg

Ethanolamine: 200.0 kg

Sodium metabisulfite: 60.0 kg

Sodium sulfite: 20.0 kg

Water: 113.0 kg

2) Process steps and process parameters

The preparation of the present invention is carried out under normal pressure:

First preheat the reactor to 80°C, add 488.0 kg of pulping black liquor with a mass fraction of 40%, 20.0 kg of hydrogen peroxide, and 5.0 kg of potassium permanganate that have been calculated, react for 20 minutes, and add 60.0 kg of formaldehyde, 20.0 kg of acrolein, continue to react for 1 hour and then raise the temperature to 160 ° C, then add 14.0 kg of monochloroacetic acid, 200.0 kg of ethanolamine, react for 1 hour, and finally add 60.0 kg of sodium metabisulfite, 20.0 kg of sodium sulfite and 113.0 kg of water mixture, react 1 After one hour, cool down and discharge the material. The prepared product is a dark brown liquid. After spray drying, a brown solid powder can be obtained. A QZP-300 pressure spray dryer is used: the inlet air temperature of the spray tower is 260°C, and the outlet air temperature is 105°C. . The molecular weight of the product is 3000.

Example 4

1) Raw materials and formulations of this example (unit - kilogram):

Alkali pulping black liquor (bamboo and bagasse mixture, mass ratio 1:1, black liquor solid content 67%): 558.0 kg;

Potassium persulfate: 40.0 kg

Formaldehyde: 33.0 kg

Acrolein: 11.0 kg

Epichlorohydrin: 8.0 kg

Dimethylamine: 30.0 kg

Triethanolamine: 30.0 kg

Sodium bisulfite: 100.0 kg

Water: 190.0 kg

2) Process steps and process parameters

The preparation of the present invention is carried out under normal pressure:

First preheat the reactor to 95°C, add 558.0 kg of pulping black liquor with a mass fraction of 41% calculated and 40.0 kg of potassium persulfate, react for 30 minutes, add 33.0 kg of formaldehyde, 11.0 kg of acrolein, and continue the reaction After 1.5 hours, the temperature was raised to 140 °C, then 8.0 kg of epichlorohydrin, 30.0 kg of dimethylamine, and 30.0 kg of triethanolamine were added, and reacted for 1 h, and finally a mixture of 100.0 kg of sodium bisulfite and 190.0 kg of water was added, and reacted for 2 h Finally, the temperature is lowered and the material is discharged. The prepared product is a dark brown liquid. After spray drying, a brown solid powder is obtained. The air inlet temperature of the spray tower is 200°C, and the outlet air temperature is 110°C. The molecular weight of the product is 41000.

Example 5

1) Raw materials and formulations of this example (unit - kilogram):

Alkaline eucalyptus pulp black liquor (55% solid content): 650.0 kg;

Potassium persulfate: 12.0 kg

Potassium permanganate: 3.0 kg

Acetaldehyde: 21.0 kg

Acrolein: 14.0 kg

Propylene oxide: 3.0 kg

Monochloroacetic acid: 2.0 kg

Formamide: 100.0 kg

Sodium metabisulfite: 57.0 kg

Sodium sulfite: 19.0 kg

Sodium bisulfite: 19.0 kg

Water: 100.0 kg

2) Process steps and process parameters

The preparation of the present invention is carried out under normal pressure:

First preheat the reactor to 90°C, add 650.0 kg of pulping black liquor with a mass fraction of 55% that has been calculated, 12.0 kg of potassium persulfate and 3.0 kg of potassium permanganate, react for 30 minutes, and add 21.0 kg of acetaldehyde , 14.0 kg of acrolein, continue to react for 2 hours, then heat up to 140 °C, then add 3.0 kg of epichlorohydrin, 2.0 kg of monochloroacetic acid, 100.0 kg of formamide, react for 1.5 h, and finally add 57.0 kg of sodium metabisulfite, 19.0 kg of sodium sulfite , a mixture of 19.0 kg of sodium bisulfite and 100.0 kg of water, reacted for 2 hours, cooled and discharged, the prepared product was a dark brown liquid, and after spray drying, a brown solid powder was obtained, and the air inlet temperature of the spray tower was 230°C , The outlet air temperature is 90°C. The molecular weight of the product is 31300.

Example 6

1) Raw materials and formulations of this example (unit - kilogram):

Alkaline masson pine pulping black liquor (46% solid content): 552.0 kg

Hydrogen peroxide: 24.0 kg

Potassium ferrate: 6.0 kg

Acetaldehyde: 54.0 kg

Ethylene oxide: 36.0 kg

Epichlorohydrin: 18.0 kg

Diethanolamine: 28.0 kg

Ethylenediamine: 56.0 kg

Chlorosulfonic acid: 102.0 kg

Water: 124.0 kg

2) Process steps and process parameters

The preparation of the present invention is carried out under normal pressure:

First preheat the reactor to 70°C, add 552.0 kg of pulping black liquor with a mass fraction of 57% that has been calculated, 24.0 kg of hydrogen peroxide and 6.0 kg of potassium ferrate, react for 30 minutes, add 54.0 kg of acetaldehyde, After continuing to react for 2 h, the temperature was raised to 140 °C, then 36.0 kg of ethylene oxide, 18.0 kg of epichlorohydrin, 28.0 kg of diethanolamine, and 56.0 kg of ethylenediamine were added for 1 h, and finally 102.0 kg of chlorosulfonic acid and 124.0 kg of Kilogram of water mixture, react for 0.5 h, cool down and discharge, the prepared product is a dark brown liquid, after spray drying, a brown solid powder can be obtained, the spray tower inlet air temperature is 230°C, and the outlet air temperature is 80°C). The molecular weight of the product is 23200.

Example 7

1) Raw materials and formulations of this example (unit - kilogram):

Alkaline birch pulp black liquor (52% solid content): 462.0 kg

Potassium ferrate: 8.0 kg

Paraformaldehyde: 30.0 kg

Hexadecane bromide: 10.0 kg

Ethylenediamine: 65.0 kg

Chlorosulfonic acid: 125.0 kg

Water: 300.0 kg

2) Process steps and process parameters

The preparation of the present invention is carried out under normal pressure:

First preheat the reactor to 90°C, add 462.0 kg of pulping black liquor with a mass fraction of 52% and 8.0 kg of potassium ferrate that have been calculated, react for 10 minutes, add 30.0 kg of paraformaldehyde to continue the reaction for 2 hours, and then raise the temperature to 100°C, then slowly add a mixture of 10.0 kg of hexadecane bromide, 65.0 kg of ethylenediamine, 125.0 kg of chlorosulfonic acid and 300.0 kg of water, react for 1 hour, cool down and discharge, the prepared product is a dark brown liquid. The molecular weight of the product is 19000.

Performance Testing

The thermal stability is tested and rated according to HG/T 3507-2008 "Sodium Lignosulfonate Dispersant" and HG/T 3399-2001 "Determination of Dye Diffusion Properties". See Figure 1 and Figure 2 for details

The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.

Claims (10)

1. modified lignin resin dispersed dye dispersion agent is characterized in that: the raw material of described dispersed dye dispersion agent is formed and mass fraction is:

Black liquor of pulp making: 45.0 parts～74.0 parts

Oxygenant: 0.5 part～4.0 parts

Aldehyde compound: 3.0 parts～8.0 parts

Negatively charged ion etherifying agent: 0.5 part～5.4 parts

Aminated compounds: 2.6 parts～20.0 parts

Sulphonating agent: 8.0 parts～18.0 parts

Water: 10.0 parts～30.0 parts.

2. a kind of modified lignin resin dispersed dye dispersion agent according to claim 1, it is characterized in that: the relative molecular mass of described dispersion agent is 3000 ~ 41000, is chocolate thick liquid or chocolate brown powder.

3. a kind of modified lignin resin dispersed dye dispersion agent according to claim 1 is characterized in that: more than 4 grades, polyamide fibre, terylene and cotton staining are more than 4 grades at the heat-resistant stability of 130 ℃ and 150 ℃ for described dispersion agent, and dispersion force is greater than 95%.

4. the preparation technology of a modified lignin resin dispersed dye dispersion agent as claimed in claim 1, it is characterized in that: described preparation technology's concrete steps are:

Black liquor of pulp making and oxygenant are reacted 10～30min under 40～95 ℃ temperature, add aldehyde compound, continue to be warming up to 90～160 ℃ behind reaction 0.5～2 h, add the mixture that adds sulphonating agent and water behind negatively charged ion etherifying agent and aminated compounds reaction 0.5～1.5 h then, behind reaction 0.5～2 h, make described dispersion agent, prepared dispersion agent is a chocolate liquid, by promptly getting the brown solid powder after the spraying drying; Above-mentioned preparation is to carry out under normal pressure.

5. according to claim 1 or 4 described modified lignin resin dispersed dye dispersion agent and preparation technologies thereof, it is characterized in that: the preparation method of described black liquor of pulp making is: select for use in bamboo, bagasse, straw, wheat straw, hybrid giant napier, Stem of Lovely Achnatherum, Qu Liu, toothed oak wood, poplar, reed, Eucalyptus, birch, the Pinus massoniana Lamb one or more to prepare black liquor of pulp making by alkaline process or sulphate process, the solid content of black liquor is 8%～75%, wherein content of lignin is 9%～45%, and density is 1.13～1.51 g/mL.

6. according to claim 1 or 4 described modified lignin resin dispersed dye dispersion agent and preparation technologies thereof, it is characterized in that: described oxygenant is one or more in potassium permanganate, hydrogen peroxide, potassium ferrate, sodium peroxide, Potassium Persulphate, Sodium Persulfate, ammonium persulphate, the clorox.

7. according to claim 1 or 4 described modified lignin resin dispersed dye dispersion agent and preparation technologies thereof, it is characterized in that: described aldehyde compound is formaldehyde, acetaldehyde, glutaraldehyde, propenal, succinic aldehyde, melamine formaldehyde (MF), trioxymethylene, in the Paraformaldehyde 96 one or more.

8. according to claim 1 or 4 described modified lignin resin dispersed dye dispersion agent and preparation technologies thereof, it is characterized in that: described negatively charged ion etherifying agent is one or more in oxyethane, propylene oxide, epoxy chloropropane, bromohexadecane, the Monochloro Acetic Acid.

9. according to claim 1 or 4 described modified lignin resin dispersed dye dispersion agent and preparation technologies thereof, it is characterized in that: described aminated compounds is one or more in dimethylamine, quadrol, thanomin, diethanolamine, trolamine, methane amide, ethanamide, diethylenetriamine, the phenylenediamine.

10. according to claim 1 or 4 described modified lignin resin dispersed dye dispersion agent and preparation technologies thereof, it is characterized in that: described sulphonating agent is one or more in S-WAT, inferior sour hydrogen sodium, chlorsulfonic acid, Sodium Pyrosulfite, sodium isethionate, ammonium sulphite, the thionamic acid.

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