CN115181216B - Retanning agent and preparation method thereof - Google Patents

Retanning agent and preparation method thereof Download PDF

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CN115181216B
CN115181216B CN202211029244.3A CN202211029244A CN115181216B CN 115181216 B CN115181216 B CN 115181216B CN 202211029244 A CN202211029244 A CN 202211029244A CN 115181216 B CN115181216 B CN 115181216B
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dihydroxyethyl
reaction
self
maleamic acid
water
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CN115181216A (en
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冯练享
王顺平
曲树光
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Qihe Leahou Chemical Industry Co ltd
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Qihe Leahou Chemical Industry Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36Amides or imides
    • C08F222/38Amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/10Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of amides or imides
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00Tanning; Compositions for tanning
    • C14C3/02Chemical tanning
    • C14C3/08Chemical tanning by organic agents
    • C14C3/22Chemical tanning by organic agents using polymerisation products

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention belongs to the technical field of polymer synthesis, and provides a retanning agent and a preparation method thereof. According to the preparation method provided by the invention, N, N-dihydroxyethyl maleamic acid self-reaction esterified product, trimethylolpropane trimethacrylate and acrylic acid are used as polymerization monomers, wherein the N, N-dihydroxyethyl maleamic acid self-reaction esterified product and the trimethylolpropane trimethacrylate have a multi-active functional group structure, and the two polymerization monomers are subjected to polymerization reaction, so that the branching degree and the crosslinking degree of a final polymer can be improved, and the dendritic polymer with a network structure is synthesized. The retanning agent prepared by the invention has strong tear resistance of leather and fine grain surface of the leather after being used; furthermore, after embossing the leather has good resilience. The data of the examples show that: the tearing resistance of the retanning agent is 74.86-76.13N; the rebound resilience was good or higher, and the grain fineness was fine.

Description

Retanning agent and preparation method thereof
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a retanning agent and a preparation method thereof.
Background
In the leather industry, retanning is a production process which is critical in leather production and is known as "gold plating" for leather production. The same leather crust can be made into solid vamp leather by adopting different retanning methods and retanning agents, and soft and plump clothing leather can be produced. The retanning agent not only has important influence on leather forming performance of leather, but also plays a role in quality and grade of leather. By using different retanning agents, different styles can be imparted to the leather. It can be said that the retanning process occupies a considerable place in modern tanning production. Acrylic retanning agents are widely used because they form better crosslinks with leather and impart good filling and fullness to leather. However, acrylic retanning agents are generally obtained by polymerization or copolymerization of monomers (acrylic acid, acrylonitrile, acrylamide and methacrylic acid) under the action of an initiator (persulfates and/or peroxides); the acrylic retanning agent can cause poor tear resistance of leather and coarser grain surface of the leather after being used; moreover, the leather after embossing has poor resilience.
Disclosure of Invention
In view of the above, the present invention aims to provide a retanning agent and a preparation method thereof. The retanning agent obtained by the preparation method provided by the invention has strong tear resistance and fine grain surface of leather after being used; furthermore, after embossing the leather has good resilience.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a retanning agent, which comprises the following steps:
mixing N, N-dihydroxyethyl maleamic acid self-reaction esterified substance, an emulsifying agent, a first water-soluble initiator and water to obtain a first monomer solution;
mixing trimethylolpropane trimethacrylate and an oil-soluble initiator to obtain a second monomer solution;
adding the second monomer solution into the first monomer solution, and performing a first polymerization reaction to obtain a prepolymerization system;
sequentially adding acrylic acid and a second water-soluble initiator into the prepolymerization system to carry out a second polymerization reaction to obtain the retanning agent;
the N, N-dihydroxyethyl maleamic acid self-reaction esterified product is obtained by self-esterification reaction of N, N-dihydroxyethyl maleamic acid.
Preferably, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterified substance, the emulsifier, the first water-soluble initiator and water is 200: 5-20: 0.5: 200-800.
Preferably, the preparation method of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product comprises the following steps:
mixing diethanolamine and maleic anhydride, and carrying out amidation reaction to obtain N, N-dihydroxyethyl maleamic acid;
and mixing the N, N-dihydroxyethyl maleamic acid with an acid catalyst, and performing self-esterification reaction to obtain the N, N-dihydroxyethyl maleamic acid self-reaction esterified product.
Preferably, the emulsifier comprises one or more of maleic acid monoalkyl ester, isooctyl alcohol polyoxyethylene ether phosphate ester, fatty acid methyl ester polyoxyethylene ether, fatty acid methyl ester ethoxylate sulfonate, fatty alcohol polyoxyethylene ether carboxylate, octyl decyl glucoside, and lauryl glucoside.
Preferably, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product, the trimethylolpropane trimethacrylate and the oil-soluble initiator is 200: 33-660: 0.1 to 2.
Preferably, the temperature of the first polymerization reaction is 80-90 ℃, and the heat preservation time is 1-3 h.
Preferably, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product, the acrylic acid and the second water-soluble initiator is 200: 10-20: 0.2.
preferably, the temperature of the second polymerization reaction is 80-90 ℃, and the heat preservation time is 1-3 h.
Preferably, after the second polymerization reaction, the method further comprises cooling, adjusting the pH value to 5-7, and then adding water for dilution.
The invention also provides a retanning agent obtained by the preparation method according to the technical scheme, the active component of the retanning agent comprises N, N-dihydroxyethyl maleamic acid self-reaction esterified substance-trimethylolpropane trimethacrylate-acrylic acid dendritic polymer, and the solid content of the retanning agent is 15-35%.
The invention provides a preparation method of a retanning agent, which comprises the following steps: mixing N, N-dihydroxyethyl maleamic acid self-reaction esterified substance, an emulsifying agent, a first water-soluble initiator and water to obtain a first monomer solution; mixing trimethylolpropane trimethacrylate and an oil-soluble initiator to obtain a second monomer solution; adding the second monomer solution into the first monomer solution, and performing a first polymerization reaction to obtain a prepolymerization system; sequentially adding acrylic acid and a second water-soluble initiator into the prepolymerization system to carry out a second polymerization reaction to obtain the retanning agent; the N, N-dihydroxyethyl maleamic acid is obtained by self-esterification reaction of N, N-dihydroxyethyl maleamic acid. The preparation method provided by the invention uses the N, N-dihydroxyethyl maleamic acid self-reaction esterified product, the trimethylolpropane trimethacrylate and the acrylic acid as polymerization monomers, wherein the N, N-dihydroxyethyl maleamic acid self-reaction esterified product and the trimethylolpropane trimethacrylate have a multi-active functional group structure, and the two polymerization monomers are subjected to polymerization reaction, so that the branching degree and the crosslinking degree of a final polymer can be improved, and the dendritic polymer with a network structure can be synthesized. The retanning agent obtained by the preparation method provided by the invention has strong tear resistance of leather and fine grain surface of the leather after being used; furthermore, after embossing the leather has good resilience. The data of the examples show that: the tearing resistance of the retanning agent is 74.86-76.13N; the rebound resilience was good or higher, and the grain fineness was fine.
The invention also provides the retanning agent obtained by the preparation method of the technical scheme, and the retanning agent provided by the invention has strong tear resistance of leather and fine grain surface of leather after being used; furthermore, after embossing the leather has good resilience.
Detailed Description
The invention provides a preparation method of a retanning agent, which comprises the following steps:
mixing N, N-dihydroxyethyl maleamic acid self-reaction esterified substance, an emulsifying agent, a first water-soluble initiator and water to obtain a first monomer solution;
mixing trimethylolpropane trimethacrylate and an oil-soluble initiator to obtain a second monomer solution;
adding the second monomer solution into the first monomer solution, and performing a first polymerization reaction to obtain a prepolymerization system;
sequentially adding acrylic acid and a second water-soluble initiator into the prepolymerization system to carry out a second polymerization reaction to obtain the retanning agent;
the N, N-dihydroxyethyl maleamic acid self-reaction esterified product is obtained by the self-esterification reaction of N, N-dihydroxyethyl maleamic acid.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention mixes N, N-dihydroxyethyl maleamic acid self-reaction esterified substance, emulsifying agent, first water-soluble initiator and water to obtain first monomer solution.
In the present invention, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterification product, the emulsifier, the first water-soluble initiator and water is preferably 200: 5-20: 0.5: 200-800.
In the invention, the N, N-dihydroxyethyl maleamic acid self-reaction esterified product is obtained by self-esterification reaction of N, N-dihydroxyethyl maleamic acid.
In the present invention, the N, N-dihydroxyethyl maleamic acid self-reaction esterification product can provide a plurality of double bonds of a spatial structure to polymerize with acrylic acid, thereby forming a network-like structure, unlike the conventional acrylic polymer which is a linear polymer.
In the present invention, the preparation method of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product preferably comprises the following steps:
mixing diethanolamine and maleic anhydride, and carrying out amidation reaction to obtain N, N-dihydroxyethyl maleamic acid;
and mixing the N, N-dihydroxyethyl maleamic acid with an acid catalyst, and performing self-esterification reaction to obtain the N, N-dihydroxyethyl maleamic acid self-reaction esterified product.
The invention mixes diethanolamine and maleic anhydride, and carries out amidation reaction to obtain N, N-dihydroxyethyl maleamic acid. In the present invention, the molar ratio of diethanolamine to maleic anhydride is preferably 1:1. in the present invention, the mode of mixing the diethanolamine and maleic anhydride is preferably: the maleic anhydride was added to the diethanolamine in portions. In the present invention, the temperature of the addition is preferably 45 ℃ or less; when each maleic anhydride is added, it is preferable to ensure that the maleic anhydride of the previous batch is completely dissolved in the diethanolamine. In the present invention, the maleic anhydride is preferably completely added to diethanolamine at 1 to 6 hours, and more preferably completely added to diethanolamine at 2 hours. In the present invention, the temperature of the amidation reaction is preferably 45℃or less, and more preferably 45 ℃; the heat preservation time is preferably 1-4 h; the incubation time is preferably timed from the time when maleic anhydride addition is completed.
After the amidation reaction, the present invention preferably directly carries out the subsequent esterification reaction of the obtained amidation reaction system without any post-treatment.
In the present invention, the N, N-dihydroxyethyl maleamic acid has a structure represented by the formula:
after the N, N-dihydroxyethyl maleamic acid is obtained, the N, N-dihydroxyethyl maleamic acid and an acid catalyst are mixed and subjected to self-esterification reaction, so that the N, N-dihydroxyethyl maleamic acid self-reaction esterified product is obtained. In the present invention, the mass of the acidic catalyst is preferably 0.1 to 3% of the total mass of diethanolamine and maleic anhydride, and more preferably 1%. In the present invention, the acidic catalyst preferably includes a solid acid and/or concentrated sulfuric acid; the solid acid preferably comprises one or more of p-toluenesulfonic acid, heteropolyacid and solid super acid, and further preferably p-toluenesulfonic acid. In the present invention, the heteropoly acid preferably includes H 3 PW 12 O 40 、H 3 SiW 12 O 40 And H 3 PMo 12 O 40 One or more of the following; the solid superacid preferably comprises SO 4 2- /ZrO 2 、MoO 3 /ZrO 2 、B 2 O 3 /ZrO 2 And WO 3 /ZrO 2 One or more of the following. In the present invention, the mixing manner of the N, N-dihydroxyethyl maleamic acid and the acidic catalyst is preferably as follows: adding the acid catalyst to the N, N-dihydroxyethyl maleamic acidThe method comprises the steps of carrying out a first treatment on the surface of the The temperature of the N, N-dihydroxyethyl maleamic acid during the mixing of the N, N-dihydroxyethyl maleamic acid and the acidic catalyst is preferably 70 ℃. In the present invention, the temperature of the self-esterification reaction is preferably 120 to 200 ℃; the heat preservation time is preferably 2-6 hours.
After the self-esterification reaction, the self-esterification reaction system is preferably directly used as the N, N-dihydroxyethyl maleamic acid self-reaction esterified product without any post-treatment to participate in the subsequent preparation of the retanning agent.
In the present invention, the emulsifier preferably includes one or more of maleic acid monoalkyl ester, isooctyl alcohol polyoxyethylene ether phosphate ester, fatty acid methyl ester polyoxyethylene ether, fatty acid methyl ester ethoxylate sulfonate, fatty alcohol polyoxyethylene ether carboxylate, octyl decyl glucoside, and lauryl glucoside. In the present invention, the monoalkyl maleate preferably includes one or more of sodium dodecyl maleate, sodium tetradecyl maleate, sodium hexadecyl maleate and sodium octadecyl maleate. In the present invention, the emulsifier serves as an emulsifier for the first polymerization reaction; further, when the emulsifier is a monoalkyl maleate, the double bond in the monoalkyl maleate may participate in the polymerization reaction.
In the present invention, the first water-soluble initiator preferably includes persulfate; the persulfate salt preferably includes one or more of potassium persulfate, sodium persulfate, and ammonium persulfate. In the present invention, the first water-soluble initiator is capable of initiating the progress of the polymerization reaction.
In the present invention, the water preferably includes distilled water.
In the present invention, the mixing of the N, N-dihydroxyethyl maleamic acid self-reactive ester, the emulsifier, the first water-soluble initiator, and the water preferably comprises: after the N, N-dihydroxyethyl maleamic acid self-reaction esterified substance is subjected to first temperature rise, an emulsifying agent, a first water-soluble initiator and water are added, and second temperature rise is performed. In the present invention, the temperature of the first elevated temperature is preferably 50 to 70 ℃, and more preferably 60 ℃; the temperature of the second elevated temperature is preferably 80 to 90 ℃, and more preferably 85 ℃. In the present invention, the mixing is preferably performed under stirring.
The invention mixes trimethylol propane trimethacrylate and oil-soluble initiator to obtain second monomer solution. In the present invention, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction ester, the trimethylolpropane trimethacrylate and the oil-soluble initiator is preferably 200: 33-660: 0.1 to 2. In the present invention, the oil-soluble initiator preferably includes one or more of benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile and azobisisoheptonitrile. The method of mixing the trimethylolpropane trimethacrylate and the oil-soluble initiator is not particularly limited in the present invention, so long as the trimethylolpropane trimethacrylate and the oil-soluble initiator can be uniformly mixed. In the invention, the trimethylolpropane trimethacrylate can provide multifunctional groups, so that the final retanning agent has a network-like structure; the oil-soluble initiator can better initiate the polymerization of the water-insoluble monomer trimethylolpropane trimethacrylate and the water-soluble monomer acrylic acid.
After a first monomer solution and a second monomer solution are obtained, the second monomer solution is added into the first monomer solution to perform a first polymerization reaction, so that a prepolymerization system is obtained. In the present invention, the mode of adding the second monomer solution is preferably dropwise addition; the dripping is preferably completed within 2-5 h. In the invention, the temperature of the first polymerization reaction is preferably 80-90 ℃, and the heat preservation time is preferably 1-3 h; the heat preservation time is preferably selected from the group consisting of starting timing after the completion of the dropwise addition of the second monomer solution.
In the present invention, in the course of the first polymerization reaction, the N, N-dihydroxyethyl maleamic acid self-reaction esterification product and the trimethylolpropane trimethacrylate are polymerized.
After the first polymerization, the present invention preferably directly carries out the subsequent second polymerization of the resulting first polymerization system without any post-treatment.
After a prepolymerization system is obtained, acrylic acid and a second water-soluble initiator are sequentially added into the prepolymerization system to carry out a second polymerization reaction, so that the retanning agent is obtained. In the present invention, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterification product, the acrylic acid and the second water-soluble initiator is preferably 200: 10-20: 0.2. in the present invention, the acrylic acid is preferably used in the form of an acrylic acid solution, and the mass concentration of the acrylic acid solution is preferably 50 to 100%; the solvent of the acrylic acid solution preferably includes one or more of water, ethanol and isopropanol. In the present invention, the acrylic acid can be copolymerized with other monomers to increase the viscosity and hydrophilicity of the polymer. In the present invention, the type of the second water-soluble initiator is preferably the same as the type of the first water-soluble initiator described in the above technical scheme, and will not be described herein. In the present invention, the second water-soluble initiator is capable of reducing the residual of the monomer.
In the present invention, the acrylic acid is preferably added dropwise, and the dropwise addition is preferably completed within 0.5 to 1 hour.
In the invention, the temperature of the second polymerization reaction is preferably 80-90 ℃, and the heat preservation time is preferably 1-3 h; the incubation time is preferably selected from the group consisting of starting the timer after the addition of the second water-soluble initiator is completed.
In the invention, the second polymerization reaction can polymerize the prepolymer formed by the N, N-dihydroxyethyl maleamic acid self-reactive esterified product and the trimethylolpropane trimethacrylate with acrylic acid to further form a water-soluble network-like polymer structure.
After the second polymerization reaction, the invention preferably further comprises cooling and adjusting the pH value to 5-7, and then adding water for dilution. In the present invention, the target temperature of the temperature decrease is preferably 40 ℃. In the present invention, the agent for adjusting the pH to 5 to 7 preferably includes a neutralizing agent, and the neutralizing agent preferably includes an organic base and/or an inorganic base; the inorganic base preferably comprises one or more of sodium hydroxide, potassium hydroxide and ammonia; the organic base preferably comprises one or more of monoethanolamine, diethanolamine, triethanolamine and 2-amino-2-methyl-1-propanol. In the invention, the pH value is adjusted to 5-7, so that the water solubility of the final retanning agent can be adapted to the requirements of the tanning process.
In the present invention, the water diluted with water preferably includes distilled water; the amount of the water diluted by adding water is not particularly limited, so long as the solid content of the final retanning agent is 15% -35%.
The invention also provides the retanning agent obtained by the preparation method. In the present invention, the methylpropane trimethacrylate-acrylic acid dendrimer. In the present invention, the solid content of the retanning agent is 15% to 35%, preferably 30%.
The retanning agent and the method for producing the same according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
200 parts by weight of N, N-dihydroxyethyl maleamic acid self-reaction esterified substance is added into reaction equipment, the temperature is raised to 60 ℃, 800 parts by weight of distilled water is added, 20 parts by weight of sodium stearyl maleate and 0.5 part by weight of ammonium persulfate are stirred uniformly, and the temperature is continuously raised to 85 ℃ to obtain a first monomer solution.
330 parts by weight of trimethylolpropane trimethacrylate was added to a high-level tank, 1 part by weight of benzoyl peroxide was added thereto, and the mixture was uniformly mixed to obtain a second monomer solution.
And (3) dripping the second monomer solution in the overhead tank into the first monomer solution in the reaction equipment for 2.5h, and carrying out polymerization reaction at 80 ℃ for 1h to obtain a prepolymerization system.
10 parts by weight of acrylic acid (the acrylic acid is used in the form of an acrylic acid solution, the mass concentration of the acrylic acid solution is 50%, and the solvent is water) is added dropwise in a prepolymerization system for 0.5h, 0.2 part by weight of ammonium persulfate is added after the completion of the dropwise addition, the reaction is continued for 1h, the temperature is reduced to 40 ℃, 65 parts by weight of sodium hydroxide is added, the pH value is neutralized to 6.1, 650 parts by weight of distilled water is added, the solid content is regulated to 30%, and the retanning agent is obtained, and the appearance is yellowish-brown semitransparent viscous emulsion.
The preparation method of the N, N-dihydroxyethyl maleamic acid self-reaction esterified substance comprises the following steps:
adding diethanolamine into reaction equipment, slowly adding maleic anhydride with the same mole number in several times, controlling the temperature to 45 ℃ by using an ice bath after each maleic anhydride addition, and continuing to add after the maleic anhydride is completely dissolved in the diethanolamine, wherein the maleic anhydride is added within 2 hours, and continuing to react for 4 hours at 45 ℃ after the maleic anhydride is added, so as to obtain N, N-dihydroxyethyl maleamic acid.
Heating the obtained N, N-dihydroxyethyl maleamic acid to 70 ℃, and adding an acid catalyst p-toluenesulfonic acid; the mass of the acid catalyst is 1 percent of the total mass of the diethanolamine and the maleic anhydride, and the reaction is continued for 6 hours after the temperature is raised to 120 ℃, thus obtaining the N, N-dihydroxyethyl maleamic acid self-reaction esterified product.
Example 2
200 parts by weight of N, N-dihydroxyethyl maleamic acid self-reaction esterified substance is added into reaction equipment, the temperature is raised to 60 ℃, 200 parts by weight of distilled water is added, 5 parts by weight of fatty alcohol polyoxyethylene ether carboxylate and 0.5 part by weight of sodium persulfate are stirred uniformly, and the temperature is raised continuously to 80 ℃ to obtain a first monomer solution.
Adding 33 parts by weight of trimethylolpropane trimethacrylate into a high-level tank, adding 0.1 part by weight of azodiisobutyronitrile, and uniformly mixing to obtain a second monomer solution.
And (3) dripping the second monomer solution in the overhead tank into the first monomer solution in the reaction equipment for 2 hours, and carrying out polymerization reaction at 85 ℃ for 1 hour to obtain a prepolymerization system.
And (3) dropwise adding 20 parts by weight of pure acrylic acid into the prepolymerization system, after the completion of dropwise adding 0.2 part by weight of sodium persulfate, continuously reacting for 1 hour, cooling to 40 ℃, adding 45 parts by weight of monoethanolamine, neutralizing the pH value to 5.8, adding 510 parts by weight of distilled water, and regulating the solid content to 30%, thereby obtaining the retanning agent with a yellowish-brown semitransparent viscous emulsion appearance.
Wherein N, N-dihydroxyethyl maleamic acid self-reactive ester was prepared as in example 1.
Example 3
200 parts by weight of N, N-dihydroxyethyl maleamic acid self-reaction esterified substance is added into reaction equipment, the temperature is raised to 60 ℃, 600 parts by weight of distilled water, 15 parts by weight of lauryl glucoside and 0.5 part by weight of ammonium persulfate are added, and the mixture is uniformly stirred and continuously raised to 90 ℃ to obtain a first monomer solution.
200 parts by weight of trimethylolpropane trimethacrylate is added into a high-level tank, 1 part by weight of azodiisoheptanenitrile is added, and the mixture is uniformly mixed to obtain a second monomer solution.
And (3) dripping the second monomer solution in the overhead tank into the first monomer solution in the reaction equipment for 3 hours, and carrying out polymerization reaction at 90 ℃ for 1 hour to obtain a prepolymerization system.
15 parts by weight of acrylic acid (the acrylic acid is used in the form of an acrylic acid solution, the mass concentration of the acrylic acid solution is 95%, and the solvent is isopropanol) is dropwise added into a prepolymerization system, 0.2 part by weight of ammonium persulfate is added after the completion of the dropwise addition, the reaction is continued for 1 hour, the temperature is reduced to 40 ℃, 50 parts by weight of 2-amino-2-methyl-1-propanol is added, the pH value is neutralized to 6.3, and then 520 parts by weight of distilled water is added, the solid content is adjusted to 30%, so that the retanning agent is obtained, and the appearance is yellowish-brown semitransparent viscous emulsion.
Wherein N, N-dihydroxyethyl maleamic acid self-reactive ester was prepared as in example 1.
Comparative example 1
Acrylic resin retanning agent LEATAN TP340, manufactured by Qihe Lichu chemical Co., ltd.
Application example
Four parts of the same part of the cowhide blue wet leather are taken, the same parts are softened, retanned and chrome retanned, retanning procedures are respectively added with retanning agents of the example 1, the example 2, the example 3 and the comparative example 1 according to the conventional process operation, the addition amounts of the retanning agents are 15% of the weight of the blue wet leather, the cowhide blue wet leather is treated for 1.5 hours in a rotary drum, the temperature is 35 ℃, the cowry SS (manufactured by zither chemical Co., ltd.) is added after water drainage, the cowry blue wet leather is treated for 1 hour in the rotary drum, the temperature is 50 ℃, then formic acid with the weight of the blue wet leather being 1.2% is added for fixation, three times of addition is carried out after dilution with triple addition, each time is separated for 10 minutes, finally, vacuum drying is carried out after water washing, the tear resistance is tested by adopting an electronic tensile tester WDW-50M, and the rebound resilience and grain surface fineness are subjectively evaluated by leather making engineers, and the results are shown in table 1.
TABLE 1 effects of application of the retanning agents of examples 1 to 3 and comparative example 1
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. A process for preparing a retanning agent, comprising the steps of:
mixing N, N-dihydroxyethyl maleamic acid self-reaction esterified substance, an emulsifying agent, a first water-soluble initiator and water to obtain a first monomer solution;
mixing trimethylolpropane trimethacrylate and an oil-soluble initiator to obtain a second monomer solution;
adding the second monomer solution into the first monomer solution, and performing a first polymerization reaction to obtain a prepolymerization system;
sequentially adding acrylic acid and a second water-soluble initiator into the prepolymerization system to carry out a second polymerization reaction to obtain the retanning agent;
the N, N-dihydroxyethyl maleamic acid self-reaction esterified product is obtained by self-esterification reaction of N, N-dihydroxyethyl maleamic acid;
the preparation method of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product comprises the following steps:
mixing diethanolamine and maleic anhydride, and carrying out amidation reaction to obtain N, N-dihydroxyethyl maleamic acid;
and mixing the N, N-dihydroxyethyl maleamic acid with an acid catalyst, and performing self-esterification reaction to obtain the N, N-dihydroxyethyl maleamic acid self-reaction esterified product.
2. The preparation method according to claim 1, wherein the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction ester, the emulsifier, the first water-soluble initiator and water is 200: 5-20: 0.5: 200-800.
3. The production method according to claim 1 or 2, wherein the emulsifier comprises one or more of maleic acid monoalkyl ester, isooctyl alcohol polyoxyethylene ether phosphate, fatty acid methyl ester polyoxyethylene ether, fatty acid methyl ester ethoxylate sulfonate, fatty alcohol polyoxyethylene ether carboxylate, octyl decyl glucoside, and lauryl glucoside.
4. The preparation method according to claim 1, wherein the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction ester, the trimethylolpropane trimethacrylate and the oil-soluble initiator is 200: 33-660: 0.1 to 2.
5. The method according to claim 1 or 4, wherein the temperature of the first polymerization reaction is 80 to 90℃and the holding time is 1 to 3 hours.
6. The preparation method according to claim 1, wherein the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product, the acrylic acid and the second water-soluble initiator is 200: 10-20: 0.2.
7. the method according to claim 1 or 6, wherein the second polymerization reaction is carried out at a temperature of 80 to 90 ℃ for a time of 1 to 3 hours.
8. The method according to claim 7, wherein the second polymerization reaction is followed by cooling and adjusting the pH to 5-7, and then diluting with water.
9. Retanning agent obtainable by the process according to any one of claims 1 to 8, characterized in that the active ingredient of the retanning agent comprises N, N-dihydroxyethyl maleamic acid self-reactive esterification product-trimethylolpropane trimethacrylate-acrylic acid dendrimer, the solids content of the retanning agent being 15% to 35%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5820633A (en) * 1996-09-20 1998-10-13 Lesko; Patricia Marie Method of treating leather with improved retaining agents
CN101381457A (en) * 2007-09-05 2009-03-11 中国科学院成都有机化学有限公司 Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5820633A (en) * 1996-09-20 1998-10-13 Lesko; Patricia Marie Method of treating leather with improved retaining agents
CN101381457A (en) * 2007-09-05 2009-03-11 中国科学院成都有机化学有限公司 Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Synthesis and Application of Highly Branched Polymers as Filling-Retanning Agents;Chai, YY, 等;OURNAL OF THE SOCIETY OF LEATHER TECHNOLOGISTS AND CHEMISTS;第94卷(第5期);200-204 *
超支化丙烯酸-马来酸酐皮革复鞣剂的合成与应用;刘军海;李志洲;王俊宏;;中国皮革(第11期);48-49, 53 *
超支化聚合物增强剂的合成与表征;刘军海;王俊宏;李志洲;;林产化学与工业(第03期);95-98 *

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