CN115181216A - Retanning agent and preparation method thereof - Google Patents
Retanning agent and preparation method thereof Download PDFInfo
- Publication number
- CN115181216A CN115181216A CN202211029244.3A CN202211029244A CN115181216A CN 115181216 A CN115181216 A CN 115181216A CN 202211029244 A CN202211029244 A CN 202211029244A CN 115181216 A CN115181216 A CN 115181216A
- Authority
- CN
- China
- Prior art keywords
- dihydroxyethyl
- self
- reaction
- acid
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/06—Macromolecular 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers 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
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers 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
- C08F222/36—Amides or imides
- C08F222/38—Amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/10—Macromolecular 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
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
Landscapes
- 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. The preparation method provided by the invention takes the N, N-dihydroxyethyl maleamic acid self-reaction esterified product, trimethylolpropane trimethacrylate and 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 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, the leather has good resilience after embossing. The data of the examples show that: the tearing resistance of the retanning agent is 74.86-76.13N; the rebound resilience is not less than good, and the fineness of the grain surface is fine.
Description
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 most critical production process in leather production and is known as "spot-making" of leather. The same leather blank can be made into firm vamp leather and soft and plump clothing leather by adopting different retanning methods and retanning agents. The retanning agent not only has important influence on the leather performance of leather, but also plays a role in playing a role in improving the quality and the grade of the 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 position in modern leather production. Acrylic retanning agents are widely used because they form better crosslinks with leather, giving the leather good filling and fullness. However, acrylic retanning agents are generally obtained by polymerization or copolymerization of monomers (acrylic acid, acrylonitrile, acrylamide and methacrylic acid) under the action of initiators (persulfates and/or peroxides); after the acrylic retanning agent is used, the tear resistance of the leather is poor, and the grain surface of the leather is thick; furthermore, the leather has poor resilience after embossing.
Disclosure of Invention
In view of this, the present invention aims to provide a retanning agent and a preparation method thereof. After the retanning agent obtained by the preparation method is used, the tear resistance of leather is high, and the grain surface of the leather is fine; moreover, the leather has good resilience after embossing.
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 the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid, an emulsifier, 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 to perform 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 esterification product is obtained by carrying out self-esterification reaction on N, N-dihydroxyethyl maleamic acid.
Preferably, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product to the emulsifier to the first water-soluble initiator to the water is 200:5 to 20:0.5:200 to 800.
Preferably, the preparation method of the N, N-dihydroxyethyl maleamic acid self-reaction esterification product comprises the following steps:
mixing diethanolamine and maleic anhydride, and carrying out amidation reaction to obtain N, N-dihydroxyethyl maleamic acid;
mixing the N, N-dihydroxyethyl maleamic acid with an acid catalyst to perform self-esterification reaction, thereby obtaining the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid.
Preferably, the emulsifier comprises one or more of a monoalkyl maleate, isooctanol polyoxyethylene ether phosphate, fatty acid methyl ester polyoxyethylene ether, fatty acid methyl ester ethoxylate sulfonate, fatty alcohol polyoxyethylene ether carboxylate, octecyl glucoside, and lauryl glucoside.
Preferably, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reaction esterified product to the trimethylolpropane trimethacrylate to the oil-soluble initiator is 200:33 to 660:0.1 to 2.
Preferably, the temperature of the first polymerization reaction is 80-90 ℃, and the holding 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 to 20:0.2.
preferably, the temperature of the second polymerization reaction is 80-90 ℃, and the holding time is 1-3 h.
Preferably, after the second polymerization reaction, the steps of cooling, adjusting the pH value to 5-7 and adding water for dilution are also included.
The invention also provides the retanning agent obtained by the preparation method in the technical scheme, the active component of the retanning agent comprises N, N-dihydroxyethyl maleamic acid self-reaction esterified product-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 the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid, an emulsifier, 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 to perform 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 carrying out self-esterification reaction on the N, N-dihydroxyethyl maleamic acid. The preparation method provided by the invention takes 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 is synthesized. The retanning agent prepared 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, the leather has good resilience after embossing. The data of the examples show that: the tearing resistance of the retanning agent is 74.86-76.13N; the rebound resilience is not less than excellent, and the fineness of the grain surface is fine.
The invention also provides the retanning agent obtained by the preparation method in the technical scheme, and the retanning agent provided by the invention has strong tear resistance of leather and fine grain surface of the leather after being used; furthermore, the leather has good resilience after embossing.
Detailed Description
The invention provides a preparation method of a retanning agent, which comprises the following steps:
mixing the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid, an emulsifier, 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 to perform 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 esterification product is obtained by the self-esterification reaction of N, N-dihydroxyethyl maleamic acid.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The method comprises the step of mixing N, N-dihydroxyethyl maleamic acid self-reaction esterified substance, emulsifier, 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-reactive esterified compound, the emulsifier, the first water-soluble initiator, and water is preferably 200:5 to 20:0.5:200 to 800.
In the invention, the N, N-dihydroxyethyl maleamic acid self-reaction esterification product is obtained by carrying out self-esterification reaction on N, N-dihydroxyethyl maleamic acid.
In the present invention, the N, N-dihydroxyethyl maleamic acid self-reactive ester can provide multiple steric double bonds to polymerize with acrylic acid to form a network structure, unlike the conventional acrylic polymer which is a linear polymer.
In the present invention, the method for producing the self-reacted esterified N, N-dihydroxyethyl maleamic acid preferably comprises the steps of:
mixing diethanolamine and maleic anhydride, and carrying out amidation reaction to obtain N, N-dihydroxyethyl maleamic acid;
mixing the N, N-dihydroxyethyl maleamic acid with an acid catalyst to perform self-esterification reaction, thereby obtaining the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid.
According to the invention, diethanolamine and maleic anhydride are mixed for 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 mixing manner of diethanolamine and maleic anhydride is preferably as follows: the maleic anhydride was added to diethanolamine in portions. In the present invention, the temperature of the addition is preferably 45 ℃ or less; when each batch of maleic anhydride is added, it is preferable to ensure that the last batch of maleic anhydride is completely dissolved in diethanolamine. In the present invention, the maleic anhydride is preferably added to diethanolamine completely within 1 to 6 hours, and more preferably added to diethanolamine completely within 2 hours. In the present invention, the temperature of the amidation reaction is preferably 45 ℃ or lower, and more preferably 45 ℃; the heat preservation time is preferably 1-4 h; the incubation time is preferably timed from the completion of the maleic anhydride addition.
After the amidation reaction, the present invention preferably performs the subsequent esterification reaction directly on the obtained amidation reaction system without any post-treatment.
In the present invention, the N, N-dihydroxyethyl maleamic acid has the structure represented by the following formula:
after the N, N-dihydroxyethyl maleamic acid is obtained, the N, N-dihydroxyethyl maleamic acid and an acid catalyst are mixed for self-esterification reaction to obtain the self-reaction esterification product of the N, N-dihydroxyethyl maleamic acid. In the present invention, the mass of the acidic catalyst is preferably 0.1 to 3%, more preferably 1%, of the total mass of diethanolamine and maleic anhydride. In the present invention, the acidic catalyst preferably comprises a solid acid and/or concentrated sulfuric acid; the solid acid preferably includes 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 solid super acid 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 (a). In the present invention, the manner of mixing the N, N-dihydroxyethyl maleamic acid and the acidic catalyst is preferably: adding said acidic catalyst to said N, N-dihydroxyethyl maleamic acid; 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 invention, the temperature of the self-esterification reaction is preferably 120-200 ℃; the heat preservation time is preferably 2 to 6 hours.
After the self-esterification reaction, the obtained self-esterification reaction system is preferably directly used as the self-reaction esterified substance of the N, N-dihydroxyethyl maleamic acid to participate in the subsequent preparation of the retanning agent without any post-treatment.
In the present invention, the emulsifier preferably includes one or more of a maleic acid monoalkyl ester, isooctanol 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. 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 acts as an emulsifier for the first polymerization reaction; further, when the emulsifier is 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 a persulfate; the persulfate preferably comprises 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 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-reacting esterified product, the emulsifier, the first water-soluble initiator and water preferably comprises: after the self-reaction esterification product of the N, N-dihydroxyethyl maleamic acid is subjected to first temperature rise, an emulsifier, a first water-soluble initiator and water are added, and second temperature rise is performed. In the present invention, the temperature of the first temperature rise is preferably 50 to 70 ℃, and more preferably 60 ℃; the temperature of the second temperature rise is preferably 80 to 90 ℃, and more preferably 85 ℃. In the present invention, the mixing is preferably performed under stirring.
According to the invention, trimethylolpropane trimethacrylate and an oil-soluble initiator are mixed to obtain a second monomer solution. In the present invention, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reacted esterified product, trimethylolpropane trimethacrylate, and oil-soluble initiator is preferably 200:33 to 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 mixing mode of the trimethylolpropane trimethacrylate and the oil-soluble initiator is not particularly limited, as long as the trimethylolpropane trimethacrylate and the oil-soluble initiator can be uniformly mixed. In the invention, the trimethylolpropane trimethacrylate can provide multiple functional groups, so that the final retanning agent has a network 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 carry out a first polymerization reaction, so as to obtain a prepolymerization system. In the present invention, the second monomer solution is preferably added dropwise; the dropwise addition is preferably completed within 2 to 5 hours. In the invention, the temperature of the first polymerization reaction is preferably 80-90 ℃, and the holding time is preferably 1-3 h; the heat preservation time is preferably timed from the end of dripping of the second monomer solution.
In the present invention, in the first polymerization reaction, the self-reacted esterified N, N-dihydroxyethyl maleamic acid and trimethylolpropane trimethacrylate undergo a polymerization reaction.
After the first polymerization reaction, the present invention preferably performs the subsequent second polymerization reaction of the obtained first polymerization reaction system without any post-treatment.
After a prepolymerization system is obtained, the method sequentially adds acrylic acid and a second water-soluble initiator into the prepolymerization system to carry out a second polymerization reaction, so as to obtain the retanning agent. In the present invention, the mass ratio of the N, N-dihydroxyethyl maleamic acid self-reactive esterified product, acrylic acid, and second water-soluble initiator is preferably 200:10 to 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 comprises 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 kind of the second water-soluble initiator is preferably the same as that of the first water-soluble initiator described in the above technical solution, and is not described herein again. In the present invention, the second water-soluble initiator can reduce the residue 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 timed from the completion of the addition of the second water-soluble initiator.
In the invention, the second polymerization reaction can enable a prepolymer formed by the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid and the trihydroxypropane trimethacrylate to have polymerization reaction with acrylic acid, and further form a water-soluble network polymer structure.
After the second polymerization reaction, the method preferably further comprises the steps of cooling, adjusting the pH value to 5-7, and 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 value 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 present invention, adjusting the pH to 5 to 7 enables the water solubility of the final retanning agent to 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, as 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 technical scheme. In the present invention, a methylpropane trimethacrylate-acrylic dendrimer. In the present invention, the solid content of the retanning agent is 15% to 35%, preferably 30%.
The retanning agent and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Adding 200 parts by weight of self-reaction esterified N, N-dihydroxyethyl maleamic acid into reaction equipment, heating to 60 ℃, adding 800 parts by weight of distilled water, 20 parts by weight of sodium stearyl maleate and 0.5 part by weight of ammonium persulfate, uniformly stirring, and continuously heating to 85 ℃ to obtain a first monomer solution.
Adding 330 parts by weight of trimethylolpropane trimethacrylate into a head tank, adding 1 part by weight of benzoyl peroxide, and uniformly mixing to obtain a second monomer solution.
And (3) dropwise adding the second monomer solution in the elevated tank into the first monomer solution in the reaction equipment, completing dripping for 2.5h, and carrying out polymerization reaction for 1h at 80 ℃ to obtain a prepolymerization system.
And (2) dripping 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) into a prepolymerization system, finishing dripping within 0.5h, adding 0.2 part by weight of ammonium persulfate after finishing dripping, continuing to react for 1h, cooling to 40 ℃, adding 65 parts by weight of sodium hydroxide, neutralizing the pH value to 6.1, adding 650 parts by weight of distilled water, and adjusting the solid content to 30% to obtain the retanning agent which is a yellowish-brown semitransparent viscous emulsion in appearance.
The preparation method of the N, N-dihydroxyethyl maleamic acid self-reaction esterification product comprises the following steps:
and adding diethanolamine into reaction equipment, slowly adding maleic anhydride with the same mole number in several times, controlling the temperature to be 45 ℃ by using an ice bath after adding the maleic anhydride each time, continuously adding the maleic anhydride after completely dissolving the maleic anhydride in the diethanolamine, adding the maleic anhydride within 2h, and continuously reacting for 4h at 45 ℃ after adding the maleic anhydride to obtain the N, N-dihydroxyethyl maleamic acid.
Heating the obtained N, N-dihydroxyethyl maleamic acid to 70 ℃, and adding an acidic catalyst, namely p-toluenesulfonic acid; the mass of the acid catalyst is 1 percent of the total mass of the diethanol amine and the maleic anhydride), the temperature is continuously increased to 120 ℃ for reaction for 6 hours, and the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid is obtained.
Example 2
Adding 200 parts by weight of self-reaction esterified N, N-dihydroxyethyl maleamic acid into a reaction device, heating to 60 ℃, adding 200 parts by weight of distilled water, 5 parts by weight of fatty alcohol polyoxyethylene ether carboxylate and 0.5 part by weight of sodium persulfate, uniformly stirring, and continuously heating to 80 ℃ to obtain a first monomer solution.
Adding 33 parts by weight of trimethylolpropane trimethacrylate into the head tank, adding 0.1 part by weight of azobisisobutyronitrile, and uniformly mixing to obtain a second monomer solution.
And (3) dropwise adding the second monomer solution in the head tank into the first monomer solution in the reaction equipment, finishing dropping for 2 hours, and carrying out polymerization reaction for 1 hour at 85 ℃ to obtain a prepolymerization system.
And (2) dropwise adding 20 parts by weight of pure acrylic acid into a prepolymerization system, dropwise adding after 1 hour, adding 0.2 part by weight of sodium persulfate after dropwise adding, 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 adjusting the solid content to 30% to obtain the retanning agent which is a yellow-brown semitransparent viscous emulsion in appearance.
Wherein the preparation of the self-reacting esterified N, N-dihydroxyethyl maleamic acid was the same as in example 1.
Example 3
Adding 200 parts by weight of self-reaction esterified N, N-dihydroxyethyl maleamic acid into a reaction device, heating to 60 ℃, adding 600 parts by weight of distilled water, 15 parts by weight of lauryl glucoside and 0.5 part by weight of ammonium persulfate, uniformly stirring, and continuously heating to 90 ℃ to obtain a first monomer solution.
Adding 200 parts by weight of trimethylolpropane trimethacrylate into the head tank, adding 1 part by weight of azobisisoheptonitrile, and uniformly mixing to obtain a second monomer solution.
And (3) dropwise adding the second monomer solution in the head tank into the first monomer solution in the reaction equipment, finishing dropping for 3 hours, and carrying out polymerization reaction for 1 hour at 90 ℃ to obtain a prepolymerization system.
Dropping 15 parts by weight of acrylic acid (the acrylic acid is used in the form of acrylic acid solution, the mass concentration of the acrylic acid solution is 95 percent, and the solvent is isopropanol) into a prepolymerization system, dropping for 1h, adding 0.2 part by weight of ammonium persulfate after dropping, continuing to react for 1h, cooling to 40 ℃, adding 50 parts by weight of 2-amino-2-methyl-1-propanol, neutralizing the pH value to 6.3, adding 520 parts by weight of distilled water, and adjusting the solid content to 30 percent to obtain the retanning agent, wherein the appearance of the retanning agent is yellow-brown semitransparent viscous emulsion.
Wherein the self-reacted esterified product of N, N-dihydroxyethylmaleamic acid is prepared in the same manner as in example 1.
Comparative example 1
The acrylic resin retanning agent LEATAN TP340, produced by QIEHEY DENTIFY CHEMICAL CO.
Application example
Taking four pieces of cowhide wet blue leather at the same position, softening, retanning with chromium, neutralizing, and operating according to a conventional process, adding the retanning agents of examples 1, 2, 3 and 1 respectively in the retanning process, wherein the addition amount of the retanning agents accounts for 15% of the weight of the wet blue leather, treating the leather in a rotary drum for 1.5h at the temperature of 35 ℃, draining, then entering a fatliquoring process, adding a general fatliquoring agent BUXOM SS (produced by Qiheqian chemical industry Co., ltd.), treating the leather in the rotary drum for 1h at the temperature of 50 ℃, then adding formic acid accounting for 1.2% of the weight of the wet blue leather for fixing, diluting the formic acid with triple water, adding the formic acid for three times at an interval of 10min every time, finally washing the leather with water, taking out the leather for vacuum drying, testing the tear resistance by an electronic tensile testing machine WDW-50M, and subjectively evaluating the rebound resilience and the grain surface fineness by a tanning engineer, wherein the results are shown in Table 1.
TABLE 1 application Effect of retanning Agents of examples 1-3 and comparative example 1
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. The preparation method of the retanning agent is characterized by comprising the following steps:
mixing the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid, an emulsifier, 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 to perform 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 esterification product is obtained by carrying out self-esterification reaction on N, N-dihydroxyethyl maleamic acid.
2. The method according to claim 1, wherein the mass ratio of the self-reacted ester of N, N-dihydroxyethyl maleamic acid, the emulsifier, the first water-soluble initiator and water is 200:5 to 20:0.5:200 to 800.
3. The method according to claim 1 or 2, wherein the method for producing the self-reacted esterified N, N-dihydroxyethyl maleamic acid comprises the steps of:
mixing diethanolamine and maleic anhydride, and carrying out amidation reaction to obtain N, N-dihydroxyethyl maleamic acid;
mixing the N, N-dihydroxyethyl maleamic acid with an acid catalyst to carry out self-esterification reaction, thereby obtaining the self-reaction esterified product of the N, N-dihydroxyethyl maleamic acid.
4. The method of claim 1 or 2, wherein the emulsifier comprises one or more of a monoalkyl maleate, isooctanol 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.
5. The method according to claim 1, wherein the mass ratio of the self-reacted esterified N, N-dihydroxyethyl maleamic acid, trimethylolpropane trimethacrylate and oil-soluble initiator is 200:33 to 660:0.1 to 2.
6. The method according to claim 1 or 5, wherein the first polymerization reaction is carried out at a temperature of 80 to 90 ℃ for a holding time of 1 to 3 hours.
7. The method according to claim 1, wherein the mass ratio of the self-reacted ester of N, N-dihydroxyethyl maleamic acid, acrylic acid and the second water-soluble initiator is 200:10 to 20:0.2.
8. the process according to claim 1 or 7, wherein the temperature of the second polymerization reaction is 80 to 90 ℃ and the holding time is 1 to 3 hours.
9. The preparation method of claim 8, wherein after the second polymerization reaction, the steps of cooling, adjusting the pH value to 5-7, and adding water for dilution are further included.
10. A retanning agent obtained by the method according to any one of claims 1 to 9, characterized in that the active ingredient of the retanning agent comprises a self-reacted esterified product of N, N-dihydroxyethylmaleamic acid-trimethylolpropane trimethacrylate-acrylic acid dendrimer, and the solid content of the retanning agent is 15% to 35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211029244.3A CN115181216B (en) | 2022-08-26 | 2022-08-26 | Retanning agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211029244.3A CN115181216B (en) | 2022-08-26 | 2022-08-26 | Retanning agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115181216A true CN115181216A (en) | 2022-10-14 |
| CN115181216B CN115181216B (en) | 2023-09-26 |
Family
ID=83522953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211029244.3A Active CN115181216B (en) | 2022-08-26 | 2022-08-26 | Retanning agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115181216B (en) |
Citations (2)
| 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 |
-
2022
- 2022-08-26 CN CN202211029244.3A patent/CN115181216B/en active Active
Patent Citations (2)
| 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)
| Title |
|---|
| CHAI, YY, 等: "Synthesis and Application of Highly Branched Polymers as Filling-Retanning Agents", OURNAL OF THE SOCIETY OF LEATHER TECHNOLOGISTS AND CHEMISTS, vol. 94, no. 5, pages 200 - 204 * |
| 刘军海;李志洲;王俊宏;: "超支化丙烯酸-马来酸酐皮革复鞣剂的合成与应用", 中国皮革, no. 11, pages 48 - 49 * |
| 刘军海;王俊宏;李志洲;: "超支化聚合物增强剂的合成与表征", 林产化学与工业, no. 03, pages 95 - 98 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115181216B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0376800A (en) | Water-repellant processing of leather and raw hide | |
| EP0648846B1 (en) | Retans with softening and hydrophobic action | |
| JPH0841130A (en) | Copolymer having ethylenically unsaturated dicarboxylic acidanhydride,long-chain olefin and fluoroolefin as constituents | |
| WO1995020056A1 (en) | Aqueous solutions or dispersions of copolymers | |
| US4737549A (en) | Terpolymers of maleic acid anhydride, (meth)acrylic acid, and (meth)acrylonitrile | |
| US5575939A (en) | Process for softening/stuffing leather and fur skins | |
| DE4416877A1 (en) | Water-soluble or water-dispersible graft polymers of proteins as leather tanning agents | |
| US5567343A (en) | New leather oiling preparations and their use | |
| CN115181216A (en) | Retanning agent and preparation method thereof | |
| CN106866886A (en) | A kind of paper both sexes drying strengthening agent | |
| EP0791023B1 (en) | Process for preparing terpolymers | |
| EP0658172B2 (en) | Alkoxy group-containing copolymers and their use for retanning leather | |
| CN1826415B (en) | Preparation of leather with polymer | |
| JP3907702B2 (en) | Aqueous polymer dispersion, process for its preparation and method of using it in the manufacture of leather | |
| CN108623735A (en) | A kind of preparation method and application of no soap coating lotion | |
| EP1668041B1 (en) | Method for the production of copolymers | |
| CN111944086B (en) | Polyacrylic acid thickener and preparation method thereof | |
| CN100523224C (en) | Method for producing leather | |
| DE4214011C1 (en) | COPOLYMERISATE | |
| CN109354639A (en) | A kind of method and its application with light-initiated preparation without soap coating lotion | |
| EP2190913A1 (en) | Method for the production of aqueous formulations, aqueous formulations, and the use thereof | |
| AU684529B2 (en) | Method for improving leather treatment | |
| JP3727379B2 (en) | Novel N-allyl-substituted oligopropenyl succinic acid half amide compound and copolymer thereof, and papermaking additive containing the copolymer | |
| JP3715715B2 (en) | Novel N-allyl-substituted alkenyl succinic acid half amide compound, copolymer thereof, and papermaking additive containing the copolymer as an active ingredient | |
| JP3722879B2 (en) | Novel alkenyl succinic acid half ester compound and copolymer thereof, and paper additive containing the copolymer as an active ingredient |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |