阅读说明：本技术 一种含磺酸盐聚合物复鞣加脂剂及其制备方法 (Sulfonate-containing polymer retanning fatliquor and preparation method thereof ) 是由 卢仕 鲍亮 宋威 张袁圆 于 2021-10-15 设计创作，主要内容包括：本发明涉及皮革化学品技术领域,公开了一种含磺酸盐聚合物复鞣加脂剂及其制备方法,为各原料组分在水溶液中通过聚合反应得到的乳液,各原料组分按占乳液总量的百分比计,包括：丙烯酸10～20％,丙烯酸酯10～20％,不饱和磺酸5～10％,不饱和酰胺8～10％,乳化剂2～5％,引发剂0.5～1％。本申请的含有磺酸盐聚合物复鞣加脂剂同时具有复鞣、加脂的功能,优异的抗冻性以及耐电解质性能,还能够克服丙烯酸聚合物复鞣带来的败色现象。(The invention relates to the technical field of leather chemicals, and discloses a retanning fatliquor containing sulfonate polymers and a preparation method thereof, wherein the retanning fatliquor is emulsion obtained by polymerization reaction of raw material components in aqueous solution, and the raw material components comprise the following components in percentage by weight of the total amount of the emulsion: 10-20% of acrylic acid, 10-20% of acrylate, 5-10% of unsaturated sulfonic acid, 8-10% of unsaturated amide, 2-5% of emulsifier and 0.5-1% of initiator. The retanning fatliquor containing the sulfonate polymer has the functions of retanning and fatliquoring, excellent freezing resistance and electrolyte resistance, and can also overcome the color failure phenomenon caused by retanning of the acrylic polymer.)

1. The retanning fatliquor containing sulfonate polymer is characterized by being an emulsion obtained by carrying out polymerization reaction on raw material components in an aqueous solution, wherein the raw material components comprise the following components in percentage by weight of the total amount of the emulsion:

10-20% of acrylic acid, 10-20% of acrylate, 5-10% of unsaturated sulfonic acid, 8-10% of unsaturated amide, 2-5% of emulsifier and 0.5-1% of initiator.

2. The sulfonate-containing polymeric retanning fatliquor of claim 1, wherein the long carbon chain acrylate comprises at least one of lauryl acrylate, myristyl acrylate, cetyl acrylate, or stearyl acrylate.

3. The sulfonate-containing polymeric retanning fatliquor of claim 1, wherein the unsaturated sulfonic acid comprises at least one of vinyl sulfonic acid, allyl sulfonic acid, 2-methyl-2-sulfoethyl acrylate, or 2-acrylamido-2-methylpropane sulfonic acid.

4. The sulfonate-containing polymeric retanning fatliquor of claim 1, wherein the unsaturated amide comprises at least one of N-methacrylamide, N-dimethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, or N-methylolmethacrylamide.

5. The sulfonate-containing polymeric retanning fatliquor of claim 1, wherein the emulsifier comprises at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether, or sorbitan fatty acid ester.

6. The sulfonate-containing polymer retanning fatliquor of claim 1, wherein the initiator comprises at least one of potassium persulfate, ammonium persulfate, or sodium persulfate.

7. The sulfonate-containing polymer retanning fatliquor according to claim 1, wherein the solid content of the emulsion is 50-55%.

8. The method for preparing the sulfonate-containing polymer retanning fatliquor according to any one of claims 1 to 7, characterized by comprising the following steps:

s1 Pre-emulsion preparation

Mixing acrylic acid, long carbon chain acrylate, an emulsifier and water, and emulsifying to obtain a stable pre-emulsion;

s2 emulsion polymerization

And (3) mixing a part of the pre-emulsion and a part of the initiator, heating, dropwise adding unsaturated sulfonic acid and unsaturated amide while stirring, reacting until the emulsion turns blue, dropwise adding the rest of the pre-emulsion and the rest of the initiator, preserving heat after dropwise adding is finished, and adjusting the pH value to obtain the finished emulsion.

9. The method for preparing the sulfonate-containing polymer retanning fatliquor according to claim 8, wherein a part of the pre-emulsion accounts for 1/4-1/3 of the total amount of the pre-emulsion, and a part of the initiator accounts for 1/4-1/3 of the total amount of the initiator.

Technical Field

The invention relates to the technical field of leather chemicals, in particular to a retanning fatliquor containing sulfonate polymers and a preparation method thereof.

Background

The retanning fatliquor is one of the important chemical materials in the process of tanning production. The leather tanning agent has the functions of retanning and fatliquoring, can lubricate leather fibers, prevent the leather from being stiff and cracked, enable the leather to have corresponding toughness and softness, and keep the strength of the leather, and meanwhile, a part of fatliquoring agent combined with the chrome leather fibers can play a role in slightly supplementing tanning, filling, assisting in dyeing and fixing color, slowing down outward migration of the chrome tanning agent and the like.

Since the 60's of the 20 th century, the work on acrylic acid polymer tanning agents at home and abroad has continued since the patent publication of acrylic acid tanning agents by Rohm & Hass, usa. The acrylic polymer has small affinity to untanned leather collagen and almost no tanning effect, but chrome tanned leather and leather tanned by other metal salts have quick absorption and fixation effects on the untanned leather collagen. Therefore, acrylic polymer tanning agents are mainly used in the retanning stage. Meanwhile, the acrylic polymers have different molecular weights and different functions. The polymer with low molecular weight has good permeability and even dyeing effect, and the tanned leather has firm body, fine and smooth grain surface and good compactness. The leather tanned by the acrylic polymer tanning agent with medium molecular weight has better leather grinding performance. The leather has high molecular weight, good filling and thickening foaming performances, and can endow the leather with good fullness and softness. In addition, acrylic acid and other functional monomer copolymers can impart other properties to the retanned leather.

Long-chain alkyl has lipophilicity, and is reported as a leather fatting agent after hydrophilic modification, wanningyan et al use N-mono maleic acid octadecyl amide and octadecyl methacrylate as lipophilic monomers to carry out solution polymerization with acrylic acid to obtain a retanning fatting agent with thickening performance (preparation and performance of the wanningyan, blue-cloud army, pink dragon, maleic acid mono amide-methacrylate-acrylic acid copolymer retanning fatting agent, fine chemical engineering, 2010,27(9): 889-892). Patent publication No. CN102534060B discloses a retanning fatliquor prepared by taking long carbon chain primary aliphatic amine and acrylic acid derivatives as raw materials and adopting a one-pot method through addition, polymerization, neutralization and saponification hydrolysis reactions, wherein the components are complex, and the obtained retanning fatliquor is a mixed component of a retanning agent and a fatliquor.

The acrylic polymer tanning agent contains a large number of carboxyl groups with negative charges, and leather dyeing after retanning by the acrylic polymer tanning agent has a 'color losing effect'. In order to overcome the phenomenon of 'color fading', a tertiary amine structure is mainly introduced at present to improve the cationic property. For example, in the case of amphoteric acrylic resin retanning agent prepared by free radical polymerization of acrylic acid and methacryloyloxyethyltrimethyl ammonium chloride by Ipomoea batal et al, the softness of finished leather can be improved, and the phenomenon of color offset (synthesis and application of amphoteric acrylic resin retanning agent, Chinese leather, 2004,33(15):3-6) can be overcome. However, the amphoteric acrylic resin retanning agent has anionic-cationic interaction and the collagen structure of the leather embryo also has an anionic-cationic amphoteric structure, so that the isoelectric point balance between the leather embryo and the amphoteric retanning agent needs to be strictly controlled, which increases the difficulty of process control, and the problems of uneven penetration, excessive surface bonding and the like of the amphoteric retanning agent are easily caused.

Disclosure of Invention

< problems to be solved by the present invention >

The method is used for solving the color failure phenomenon of the existing acrylic polymer retanning agent and simultaneously improving the frost resistance and electrolyte resistance of the retanning fatliquor.

< technical solution adopted in the present invention >

Aiming at the technical problems, the invention aims to provide a polymer retanning fatliquor containing sulfonate and a preparation method thereof. The retanning fatliquor containing the sulfonate polymer has the functions of retanning and fatliquoring, excellent freezing resistance and electrolyte resistance, and can also overcome the color failure phenomenon caused by retanning of the acrylic polymer.

The specific contents are as follows:

the invention provides a sulfonate-containing polymer retanning fatliquor, which is an emulsion obtained by carrying out polymerization reaction on raw material components in an aqueous solution, wherein the raw material components comprise the following components in percentage by weight of the total amount of the emulsion:

10-20% of acrylic acid, 10-20% of acrylate, 5-10% of unsaturated sulfonic acid, 8-10% of unsaturated amide, 2-5% of emulsifier and 0.5-1% of initiator.

Secondly, the invention provides a preparation method of a sulfonate-containing polymer retanning fatliquor, which comprises the following steps:

s1 Pre-emulsion preparation

Mixing acrylic acid, long carbon chain acrylate, an emulsifier and water, and emulsifying to obtain a stable pre-emulsion;

s2 emulsion polymerization

And (3) mixing a part of the pre-emulsion and a part of the initiator, heating, dropwise adding unsaturated sulfonic acid and unsaturated amide while stirring, reacting until the emulsion turns blue, dropwise adding the rest of the pre-emulsion and the rest of the initiator, preserving heat after dropwise adding is finished, and adjusting the pH value to obtain the finished emulsion.

< technical mechanism adopted in the present invention >

(1) The amide structure is introduced into an acrylic polymer to improve the 'color losing' problem of the retanning fatliquor. Specifically, the alkalinity of the amide is very weak, and the alkalinity of the amide is much weaker than that of ammonia or amine, so that the amide structure does not cause adverse effects on the permeation uniformity of the retanning fatliquor on the leather embryo, and meanwhile, the amide structure has certain affinity to anionic dyes; the introduction of amide groups can further increase the functions of tanning agents and collagen carboxyl groups and improve fullness, and meanwhile, the amide groups have weak alkalinity and can form ionic bonds with acid groups of anionic dyes; the amide group can also form intermolecular hydrogen bond with carboxyl, hydroxyl and amino in dye molecules, and has the effect of preventing 'color fading'. Therefore, the amide structure is introduced, so that the fullness can be increased, the color losing problem can be improved, and the comprehensive performance of the retanning fatliquor can be greatly improved.

(2) The introduction of sulfonic acid groups can improve the electric medium resistance and the freezing resistance of the emulsion, and the reason is that the sulfonate is strong acid and strong alkali salt, the ionization strength is high, the zeta potential of a double electric layer of latex particles is enhanced, a stronger electrostatic repulsion effect is formed between the latex particles, and the coagulation of the latex particles is prevented; meanwhile, the product can be stored for at least 48 hours at the temperature of minus 20 ℃, and still has good fluidity when being thawed at room temperature.

< advantageous effects achieved by the present invention >

(1) The polymer is obtained by selecting and matching unsaturated sulfonic acid and unsaturated amide, and copolymerizing the unsaturated sulfonic acid and unsaturated amide with acrylic acid and octadecyl acrylate, and the polymer has retanning and fatliquoring functions;

(2) the sulfonic acid group is introduced to the polymer molecule, so that the freezing resistance and the dielectric resistance of the retanning fatliquor can be improved, and meanwhile, the polymer retanning fatliquor with uniform components is synthesized by a process method of separately dropwise adding unsaturated sulfonic acid and unsaturated amide and pre-emulsion.

(3) The problem of color loss caused by dyeing after acrylic polymer retanning can be solved by introducing an amide structure.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The invention provides a sulfonate-containing polymer retanning fatliquor, which is an emulsion obtained by carrying out polymerization reaction on raw material components in an aqueous solution, wherein the raw material components comprise the following components in percentage by weight of the total amount of the emulsion:

10-20% of acrylic acid, 10-20% of acrylate, 5-10% of unsaturated sulfonic acid, 8-10% of unsaturated amide, 2-5% of emulsifier and 0.5-1% of initiator.

In the present invention, the long carbon chain acrylate includes at least one of lauryl acrylate, myristyl acrylate, cetyl acrylate, or stearyl acrylate.

In the present invention, the unsaturated sulfonic acid includes at least one of vinylsulfonic acid, allylsulfonic acid, 2-methyl-2-propenoic acid-2-sulfoethyl ester, or 2-acrylamido-2-methylpropanesulfonic acid.

In the present invention, the unsaturated amide includes at least one of N-methacrylamide, N-dimethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, or N-methylolmethacrylamide.

In the invention, the emulsifier comprises at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether or sorbitan fatty acid ester.

In the present invention, the initiator includes at least one of potassium persulfate, ammonium persulfate, or sodium persulfate.

In the invention, the solid content of the emulsion is 50-55%.

Secondly, the invention provides a preparation method of a sulfonate-containing polymer retanning fatliquor, which comprises the following steps:

s1 Pre-emulsion preparation

Mixing acrylic acid, long carbon chain acrylate, an emulsifier and water, and emulsifying to obtain a stable pre-emulsion;

s2 emulsion polymerization

And (3) mixing a part of the pre-emulsion and a part of the initiator, heating, dropwise adding unsaturated sulfonic acid and unsaturated amide while stirring, reacting until the emulsion turns blue, dropwise adding the rest of the pre-emulsion and the rest of the initiator, preserving heat after dropwise adding is finished, and adjusting the pH value to obtain the finished emulsion.

In the invention, a part of the pre-emulsion accounts for 1/4-1/3 of the total amount of the pre-emulsion, and a part of the initiator accounts for 1/4-1/3 of the total amount of the initiator.

< example >

Example 1

A preparation method of a retanning fatliquor of a polymer containing sulfonate comprises the following steps:

mixing and emulsifying acrylic acid, octadecyl acrylate, an emulsifier (sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether in a mass ratio of 3:1) and water for 1 hour to form a stable pre-emulsion.

1/4 of the total amount of the pre-emulsion is added into the reaction kettle, 1/4 of the total amount of the sodium persulfate is added at the same time, and the temperature is increased to 75-80 ℃. Starting stirring and dropwise adding the vinyl sulfonic acid and the N, N-dimethylacrylamide aqueous solution, and starting dropwise adding the residual pre-emulsion and the sodium persulfate aqueous solution when the emulsion turns blue. Dropwise adding all the materials within 3-4h, carrying out heat preservation reaction for 1h, adding sodium hydroxide to adjust the pH of the emulsion to 7.0-8.0, and obtaining the sulfonate-containing polymer retanning fatliquor emulsion with the solid content of 50%.

Wherein, the acrylic acid accounts for 20 percent of the total mass of the emulsion, the octadecyl acrylate accounts for 10 percent of the total mass of the emulsion, the vinylsulfonic acid accounts for 5 percent of the total mass of the emulsion, the N, N-dimethylacrylamide accounts for 10 percent of the total mass of the emulsion, the emulsifying agent accounts for 5 percent of the total mass of the emulsion, and the sodium persulfate accounts for 0.5 percent of the total mass of the emulsion.

Example 2

A preparation method of a retanning fatliquor of a polymer containing sulfonate comprises the following steps:

mixing and emulsifying acrylic acid, tetradecyl acrylate, an emulsifier (fatty alcohol-polyoxyethylene ether sulfate and fatty alcohol-polyoxyethylene ether in a mass ratio of 3:2) and water for 1 hour to form a stable pre-emulsion.

1/4 of the total amount of the pre-emulsion is added into the reaction kettle, 1/4 of the total mass of ammonium persulfate is added at the same time, and the temperature is increased to 80-90 ℃. Starting stirring and dropwise adding the 2-acrylamide-2-methyl propanesulfonic acid aqueous solution, and starting dropwise adding the residual pre-emulsion and the ammonium persulfate aqueous solution when the emulsion turns blue. Dropwise adding all the materials within 3-4h, carrying out heat preservation reaction for 1h, adding sodium hydroxide to adjust the pH of the emulsion to 6.5-7.5, and obtaining the sulfonate-containing polymer retanning fatliquor emulsion with the solid content of 53%.

Wherein, the acrylic acid accounts for 10 percent of the total mass of the emulsion, the tetradecyl acrylate accounts for 20 percent of the total mass of the emulsion, the 2-methyl-2-acrylic acid-2-sulfoethyl ester accounts for 10 percent of the total mass of the emulsion, the 2-acrylamide-2-methylpropanesulfonic acid accounts for 10 percent of the total mass of the emulsion, the emulsifier accounts for 2 percent of the total mass of the emulsion, and the ammonium persulfate accounts for 1 percent of the total mass of the emulsion.

Example 3

A preparation method of a retanning fatliquor of a polymer containing sulfonate comprises the following steps:

mixing and emulsifying acrylic acid, cetyl acrylate, an emulsifier (sodium dodecyl benzene sulfonate and sorbitan fatty acid ester in a mass ratio of 4:1) and water for 1 hour to form a stable pre-emulsion.

1/4 mass percent of the pre-emulsion is added into the reaction kettle, 1/4 mass percent of the total mass of the potassium persulfate is added at the same time, and the temperature is raised to 70-90 ℃. Starting stirring and dropwise adding an allyl sulfonic acid and N-methacrylamide aqueous solution, and starting dropwise adding the rest pre-emulsion and a potassium persulfate aqueous solution when the emulsion turns blue. Dropwise adding all the materials within 3-4h, carrying out heat preservation reaction for 1h, adding sodium hydroxide to adjust the pH of the emulsion to 7.5-8.0, and thus obtaining the sulfonate-containing retanning fatliquor emulsion with the solid content of 52%.

Wherein, acrylic acid accounts for 18 percent of the total mass of the emulsion, long carbon chain acrylic ester accounts for 10 percent of the total mass of the emulsion, allyl sulfonic acid accounts for 10 percent of the total mass of the emulsion, N-methacrylamide accounts for 8 percent of the total mass of the emulsion, emulsifying agent accounts for 5 percent of the total mass of the emulsion, and potassium persulfate accounts for 0.8 percent of the total mass of the emulsion.

Example 4

A preparation method of a retanning fatliquor of a polymer containing sulfonate comprises the following steps:

mixing and emulsifying acrylic acid, lauryl acrylate, an emulsifier (fatty alcohol polyoxyethylene ether sulfur and sorbitan fatty acid ester according to the mass ratio of 2:2) and water for 1 hour to form a stable pre-emulsion.

1/4 of the mass of the pre-emulsion is added into the reaction kettle, 1/4 of the total mass of ammonium persulfate is added at the same time, and the temperature is increased to 80-90 ℃. Starting stirring and dropwise adding the 2-methyl-2-acrylic acid-2-sulfoethyl ester and the N-hydroxymethyl methacrylamide aqueous solution, and starting dropwise adding the residual pre-emulsion ammonium persulfate aqueous solution when the emulsion turns blue. Dropwise adding all the materials within 3-4h, carrying out heat preservation reaction for 1h, adding sodium hydroxide to adjust the pH of the emulsion to 6.5-8.0, and thus obtaining the sulfonate-containing polymer retanning fatliquor emulsion with the solid content of 55%.

Wherein, the acrylic acid accounts for 20 percent of the total mass of the emulsion, the lauryl acrylate accounts for 15 percent of the total mass of the emulsion, the 2-methyl-2-acrylic acid-2-sulfoethyl ester accounts for 8 percent of the total mass of the emulsion, the N-hydroxymethyl methacrylamide accounts for 8 percent of the total mass of the emulsion, the emulsifier accounts for 3 percent of the total mass of the emulsion, and the ammonium persulfate accounts for 1 percent of the total mass of the emulsion.

< comparative example >

Comparative example 1

This comparative example differs from example 1 in that no N, N-dimethylacrylamide was added.

Comparative example 2

This comparative example differs from example 1 in that no vinylsulfonic acid was added.

< test example >

The samples were tested for freeze-thaw stability, electrolyte stability, color and fullness using examples 1-4 and comparative examples 1-2, respectively.

Test example 1 Freeze-thaw stability and electrolyte stability measurement

The emulsion was subjected to freeze-thaw stability testing: 100g of the sample emulsion is placed in a refrigerator at the temperature of-20 ℃ for freezing for 48h, taken out and placed at room temperature for melting, and the experimental results are shown in Table 1.

The emulsion was subjected to electrolyte stability testing: a10 mL graduated tube is taken, 5mL of sample emulsion is added by a dropper, 1mL of 5% calcium chloride solution is added, the mixture is shaken up and placed for 48 hours for observation. The results of the experiment are shown in table 1.

TABLE 1 emulsion Performance test results

Test example 2 application experiment

The emulsions obtained in examples 1 to 4 and comparative examples 1 and 2 were used to retan, fatliquify and dye wet cattle blue, the operating process is shown in table 2 and the results of the application are shown in table 3. In Table 2, cattle blue wet leather is from Tanshixing group of Zhejiang, Japan, Luconyl Black 0066 is from Pasteff, Germany, degreasing agent DOC, interstitial remover TJ-A180, rewetting protectant BSP, stain remover TJ-A971, chrome tanning agent TJ-T125 and high efficiency neutralizer TJ-R819 are all from Tanshijiang new materials, and other chemicals are from Corrong reagent. All chemicals were used as a percentage of the wet blue weight.

TABLE 2 emulsion application experiment

TABLE 3 results of emulsion application

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.