CN111118237A - Light-resistant fatting agent intermediate - Google Patents
Light-resistant fatting agent intermediate Download PDFInfo
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- CN111118237A CN111118237A CN201911357209.2A CN201911357209A CN111118237A CN 111118237 A CN111118237 A CN 111118237A CN 201911357209 A CN201911357209 A CN 201911357209A CN 111118237 A CN111118237 A CN 111118237A
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- 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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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Abstract
The invention discloses a light-resistant fatliquor intermediate, which takes first saturated fatty acid and diethanol amine as raw materials, wherein the long-chain first saturated fatty acid is one of lauric acid, myristic acid and palmitic acid; after the reaction is finished, reacting with a second saturated fatty acid to obtain the compound; the second saturated fatty acid is one of lauric acid, myristic acid, palmitic acid and 12-hydroxystearic acid. The synthesized light-resistant fatting agent intermediate not only has better light resistance, but also has a fatty acid amide structure and a fatty acid ester structure in molecules, and contains hydroxyl, so that the compatibility with other various fatting agents is improved, and the intermediate can continuously participate in the reaction. The molecules contain acylamino and ester groups, and can be used as raw materials to be compounded into various leather fatting agents to improve the compounding effect and the fatting performance; the hydroxyl with reactivity in the molecule can also be used as a reaction oil material for preparing the phosphorylation fatting agent and the sulfonic succinic acid ester fatting agent, and the application range is wide.
Description
Technical Field
The invention relates to the technical field of leather chemical industry, in particular to a light-resistant fatting agent intermediate.
Background
The leather needs to go through a series of processing procedures from raw leather to finished leather products, wherein the greasing procedure is one of the key procedures of the leather-making processing, not only determines the softness, fullness and elasticity of finished leather, but also influences the physical and mechanical properties, such as hand feeling characteristics, water absorbability, water vapor permeability, air permeability and the like of the finished leather, and also greatly influences the physical and mechanical properties, such as tensile strength, extensibility and the like of the leather. In recent years, fatliquoring agents are developed towards the functionalization direction so as to meet the higher and higher requirements of people on leather products, and special service performances such as water resistance, oil resistance, pollution resistance, flame retardance, atomization resistance, light resistance and the like are endowed to leather through fatliquoring.
The long-chain alkyl alcohol amide surfactant is a novel green surfactant and has excellent dispersing, solubilizing, thickening and other properties; the leather finishing agent is widely applied to textile auxiliaries, leather fatting agents, hand feeling agents of leather finishing materials and the like. The long-chain alkylolamides used for preparing the leather fatting agent at present are prepared by amidation reaction of alcohol amine and natural grease or fatty acid; such as long chain alkylolamides prepared from rapeseed oil fatty acids. The long chain of the alkylolamide contains carbon-carbon double bonds, is easy to oxidize, has high iodine value, and the prepared fatting agent has poor light resistance and is not suitable for light-colored leather; and the alkylolamides can not be directly used in the compounding process of the fatting agent, so that the application range of the alkylolamides is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a light-resistant fatliquor intermediate which has high saturation, low iodine value, good reactivity and high light resistance.
In order to achieve the purpose, the invention provides the following technical scheme: a light-resistant fatting agent intermediate has a structural formula shown in the specification
Wherein R is1Is CH3(CH2)10、CH3(CH2)12And CH3(CH2)14Any one of the above; r2Is CH3(CH2)10、CH3(CH2)12、CH3(CH2)14And CH3(CH2)5CHOH(CH2)10Any one of them.
As a further improvement of the invention, the preparation method of the light-resistant fatliquor intermediate comprises the following steps:
the method comprises the following steps: adding diethanolamine and first saturated fatty acid into a reaction container, stirring and mixing, uniformly mixing to form a first mixed solution, and then heating for reaction;
step two: adding a second saturated fatty acid and a catalyst into the reaction container in the first step at the temperature of 75-85 ℃, stirring and mixing, uniformly mixing to form a second mixed solution, and then heating for reaction; and after the reaction is finished, discharging at the temperature of 65-75 ℃ to obtain the light-resistant fatliquoring agent intermediate.
As a further improvement of the present invention, the first saturated fatty acid is any one of lauric acid, myristic acid, and palmitic acid.
As a further improvement of the present invention, the second saturated fatty acid is any one of lauric acid, myristic acid, palmitic acid, and 12-hydroxystearic acid.
As a further improvement of the invention, the catalyst is p-toluenesulfonic acid.
As a further development of the invention, the mass ratio between diethanolamine and first saturated fatty acids in step one is 1: 0.9-1.1.
As a further improvement of the invention, the heating for reaction in the first step means that the temperature of the first mixed solution is raised to 120-150 ℃ for reaction until the amine value in the first mixed solution is less than or equal to 10.0 mgKOH/g.
As a further development of the invention, the ratio of the amount of substance of the second saturated fatty acid in step two to the amount of substance of the diethanolamine in step one is from 0.9 to 1.1: 1.
As a further improvement of the invention, the mass of the catalyst in the second step is 0.2-0.5% of the mass of the second saturated fatty acid in the second step.
As a further improvement of the invention, the heating for reaction in the second step means that the temperature of the second mixed solution is raised to 120-150 ℃ for reaction until the amine value in the second mixed solution is less than or equal to 5.0mgKOH/g and the acid value is less than or equal to 10.0 mgKOH/g.
The invention has the beneficial effects that: taking first saturated fatty acid and diethanolamine as raw materials, wherein the long-chain first saturated fatty acid is selected from one of lauric acid, myristic acid and palmitic acid; after the reaction is finished, reacting with a second saturated fatty acid to obtain the compound; the second saturated fatty acid is one of lauric acid, myristic acid, palmitic acid and 12-hydroxystearic acid. The synthesized light-resistant fatting agent intermediate not only has better light resistance, but also has a fatty acid amide structure and a fatty acid ester structure in molecules, and contains hydroxyl, so that the compatibility with other various fatting agents is improved, and the intermediate can continuously participate in the reaction. The fatty acid amide ester as the intermediate of the light-resistant fatting agent prepared by the invention is cream-like in appearance, contains acylamino and ester group in the molecule, and can be used as a raw material to be compounded into various leather fatting agents to improve the compounding effect and the fatting performance; hydroxyl with reactivity in molecules can also be used as a reaction oil material for preparing the phosphorylation fatting agent and the sulfosuccinate fatting agent; all the above can endow the leather with better softness and natural luster. The light-resistant fatting agent intermediate fatty acid amide ester prepared by the invention does not need to add other solvents or dispersing agents in the preparation process, is environment-friendly, and has the purity of more than 90 percent through amidation and esterification reactions; still have a small amount of by-products to exist, also have certain compounding and fat liquoring effect, need not to separate, realize the zero release process, belong to the clean production technology.
Detailed Description
Example 1
A preparation method of a light-resistant fatliquor intermediate comprises the following steps:
the method comprises the following steps: adding 1mol of diethanolamine and 0.95mol of lauric acid into a reaction container, stirring and mixing, and forming a first mixed solution after uniformly mixing; then the temperature of the first mixed solution is raised to 140 ℃ for reaction until the amine value in the first mixed solution is less than or equal to 10.0 mgKOH/g;
step two: adding 1.1mol of lauric acid and catalyst p-toluenesulfonic acid into the reaction container in the first step at the temperature of 80 ℃, stirring and mixing, and uniformly mixing to form a second mixed solution; then, the temperature of the second mixed solution is raised to 140 ℃, and then the second mixed solution is reacted until the amine value in the second mixed solution is less than or equal to 5.0mgKOH/g and the acid value in the second mixed solution is less than or equal to 10.0 mgKOH/g; and after the reaction is finished, discharging at the temperature of 70 ℃ to obtain the light-resistant fatliquoring agent intermediate. (wherein the mass of the catalyst in the second step is 0.35 percent of the mass of the lauric acid in the second step); characterization data:1H NMR(400MHz,CDCl3)δ5.06-5.01(m,2H),4.75-4.71(m,1H),3.76-3.74(m,2H),3.57-3.53(m,2H),3.33-3.29(m,4H),2.18-2.15(m,2H),1.85-1.82(m,2H),1.46-1.43(m,2H),1.28-1.21(m,32H),0.82-0.78(m,6H)13C NMR(125MHz,CDCl3) δ 189.8,172.1,81.6,70.2,58.3,52.2,46.4,33.7,31.6,31.2,29.9,29.4,29.1,28.5,28.2,22.1, 13.7; the yield was 94%
The structural formula of the light-resistant fatting agent intermediate is shown in the specification
Example 2
A preparation method of a light-resistant fatliquor intermediate comprises the following steps:
the method comprises the following steps: adding 1mol of diethanolamine and 0.95mol of myristic acid into a reaction container, stirring and mixing, and forming a first mixed solution after uniformly mixing; then the temperature of the first mixed solution is raised to 140 ℃ for reaction until the amine value in the first mixed solution is less than or equal to 10.0 mgKOH/g;
step two: adding 1.1mol of myristic acid and catalyst p-toluenesulfonic acid into the reaction container in the first step at the temperature of 80 ℃, stirring and mixing, and uniformly mixing to form a second mixed solution; then, the temperature of the second mixed solution is raised to 140 ℃, and then the second mixed solution is reacted until the amine value in the second mixed solution is less than or equal to 5.0mgKOH/g and the acid value in the second mixed solution is less than or equal to 10.0 mgKOH/g; and after the reaction is finished, discharging at the temperature of 70 ℃ to obtain the light-resistant fatliquoring agent intermediate. (wherein the mass of the catalyst in the second step is 0.3 percent of that of the myristic acid in the second step);
characterization data:1H NMR(400MHz,CDCl3)δ5.01-5.07(m,1H),4.97-4.93(m,1H),4.71-4.68(m,1H),3.69-3.66(m,2H),3.57-3.52(m,2H),3.33-3.30(m,4H),2.23-2.21(m,2H),1.88-1.84(m,2H),1.47-1.44(m,2H),1.28-1.24(m,14H),1.20-1.17(m,26H),0.81-0.78(m,6H)；
13C NMR(125MHz,CDCl3) δ 189.8,172.1,81.7,70.2,58.2,52.3,46.4,33.9,31.8,31.6,30.1,29.8,29.5,29.4,29.1,28.5,28.2,26.4,22,3, 13.6; the yield is 92%
The structural formula of the light-resistant fatting agent intermediate is shown in the specification
Example 3
A preparation method of a light-resistant fatliquor intermediate comprises the following steps:
the method comprises the following steps: adding 1mol of diethanolamine and 0.95mol of palmitic acid into a reaction vessel, stirring and mixing, and uniformly mixing to form a first mixed solution; then the temperature of the first mixed solution is raised to 140 ℃ for reaction until the amine value in the first mixed solution is less than or equal to 10.0 mgKOH/g;
step two: adding 1.1mol of 12-hydroxystearic acid and a catalyst p-toluenesulfonic acid into the reaction container in the first step at the temperature of 80 ℃, stirring and mixing, and uniformly mixing to form a second mixed solution; then, the temperature of the second mixed solution is raised to 140 ℃, and then the second mixed solution is reacted until the amine value in the second mixed solution is less than or equal to 5.0mgKOH/g and the acid value in the second mixed solution is less than or equal to 10.0 mgKOH/g; and after the reaction is finished, discharging at the temperature of 70 ℃ to obtain the light-resistant fatliquoring agent intermediate. (wherein the mass of the catalyst in the second step is 0.4 percent of the mass of the 12-hydroxystearic acid in the second step); the yield is 91%;
the structural formula of the light-resistant fatting agent intermediate is shown in the specification
The reaction of the invention is divided into two steps:
first step of
Wherein R is1COOH is the first saturated stearic acid
Second step of
Wherein R is2COOH is second saturated stearic acid;
the invention relates to a light-resistant fatliquor intermediate, which takes first saturated fatty acid and diethanol amine as raw materials, wherein the long-chain first saturated fatty acid is one of lauric acid, myristic acid and palmitic acid; after the reaction is finished, reacting with a second saturated fatty acid to obtain the compound; the second saturated fatty acid is one of lauric acid, myristic acid, palmitic acid and 12-hydroxystearic acid. The synthesized light-resistant fatting agent intermediate not only has better light resistance, but also has a fatty acid amide structure and a fatty acid ester structure in molecules, and contains hydroxyl, so that the compatibility with other various fatting agents is improved, and the intermediate can continuously participate in the reaction. The intermediate of the fatting agent prepared by the invention mainly contains fatty acid amide ester, and the molecular structure general formula is as follows:
compared with the prior art, the invention adopts two-stage reaction to prepare the fatting agent intermediate saturated fatty acid amide ester; in the first stage, amino in diethanolamine and carboxyl in first saturated stearic acid are subjected to acylation reaction; the second stage, mainly the hydroxyl groups on the fatty acid amide molecules and the second saturated fatty acids (R) of the product of the first stage2COOH) to produce fatty acid amide ester. Meanwhile, the reaction product also contains a small amount of other by-products such as fatty acid monoamide, fatty acid monoester and the like, but all of them can beThe leather greasing agent is used as a raw material for compounding or reacting, and does not need to be separated and removed.
The catalyst p-toluenesulfonic acid is added in the second reaction stage, so that the esterification efficiency can be effectively improved, the reaction time is shortened, and the energy consumption is saved.
The fatty acid amide ester as the intermediate of the light-resistant fatting agent prepared by the invention is cream-like in appearance, contains acylamino and ester group in the molecule, and can be used as a raw material to be compounded into various leather fatting agents to improve the compounding effect and the fatting performance; hydroxyl with reactivity in molecules can also be used as a reaction oil material for preparing the phosphorylation fatting agent and the sulfosuccinate fatting agent; all the above can endow the leather with better softness and natural luster.
The light-resistant fatting agent intermediate fatty acid amide ester prepared by the invention does not need to add other solvents or dispersing agents in the preparation process, is environment-friendly, and has the purity of more than 90 percent through amidation and esterification reactions; still have a small amount of by-products to exist, also have certain compounding and fat liquoring effect, need not to separate, realize the zero release process, belong to the clean production technology.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (10)
1. A light-resistant fatting agent intermediate is characterized in that: the structural formula of the light-resistant fatting agent intermediate is shown in the specification
Wherein R is1Is CH3(CH2)10、CH3(CH2)12And CH3(CH2)14Any one of the above; r2Is CH3(CH2)10、CH3(CH2)12、CH3(CH2)14And CH3(CH2)5CHOH(CH2)10Any one of them.
2. The photostable fatliquor intermediate according to claim 1, wherein: the preparation method of the light-resistant fatliquor intermediate comprises the following steps:
the method comprises the following steps: adding diethanolamine and first saturated fatty acid into a reaction container, stirring and mixing, uniformly mixing to form a first mixed solution, and then heating for reaction;
step two: adding a second saturated fatty acid and a catalyst into the reaction container in the first step at the temperature of 75-85 ℃, stirring and mixing, uniformly mixing to form a second mixed solution, and then heating for reaction; and after the reaction is finished, discharging at the temperature of 65-75 ℃ to obtain the light-resistant fatliquoring agent intermediate.
3. A photostable fatliquor intermediate as claimed in claim 2, wherein: the first saturated fatty acid is any one of lauric acid, myristic acid and palmitic acid.
4. A photostable fatliquor intermediate as claimed in claim 3, wherein: the second saturated fatty acid is any one of lauric acid, myristic acid, palmitic acid and 12-hydroxystearic acid.
5. The photostable fatliquor intermediate according to claim 4, wherein: the catalyst is p-toluenesulfonic acid.
6. The method for preparing the intermediate of the light-resistant fatliquor according to claim 5, wherein the method comprises the following steps: in the first step, the mass ratio of the diethanolamine to the first saturated fatty acid is 1: 0.9-1.1.
7. The method for preparing the intermediate of the light-resistant fatliquor according to claim 6, wherein the method comprises the following steps: the heating for reaction in the first step means that the temperature of the first mixed solution is raised to 120-150 ℃ for reaction until the amine value in the first mixed solution is less than or equal to 10.0 mgKOH/g.
8. The method for preparing the intermediate of the light-resistant fatliquor according to claim 7, wherein the method comprises the following steps: the ratio of the amount of the second saturated fatty acid substance in the second step to the amount of the diethanolamine substance in the first step is 0.9-1.1: 1.
9. The method for preparing a light-fast fatliquor intermediate according to claim 8, wherein: the mass of the catalyst in the second step is 0.2-0.5% of that of the second saturated fatty acid in the second step.
10. The method for preparing a light-fast fatliquor intermediate according to claim 9, wherein: the heating for reaction in the second step means that the temperature of the second mixed solution is raised to 150 ℃ of 120-.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430306A (en) * | 2021-07-14 | 2021-09-24 | 陕西科技大学 | Anti-yellowing titanium dioxide/fatty acid-based leather fatliquoring agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104831004A (en) * | 2015-05-30 | 2015-08-12 | 山东黎宁科技新材料有限公司 | Novel synthetic cationic vegetable oil fat liquor and preparation method thereof |
| CN107058649A (en) * | 2017-03-31 | 2017-08-18 | 温州大学 | A kind of hydroxy stearate acid polyethylene glycol dibasic acid esters of fatting agent intermediate 12 and preparation method thereof |
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2019
- 2019-12-25 CN CN201911357209.2A patent/CN111118237B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104831004A (en) * | 2015-05-30 | 2015-08-12 | 山东黎宁科技新材料有限公司 | Novel synthetic cationic vegetable oil fat liquor and preparation method thereof |
| CN107058649A (en) * | 2017-03-31 | 2017-08-18 | 温州大学 | A kind of hydroxy stearate acid polyethylene glycol dibasic acid esters of fatting agent intermediate 12 and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郑延成: "脂肪酸二乙醇胺类表面活性剂合成研究", 《长江大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113430306A (en) * | 2021-07-14 | 2021-09-24 | 陕西科技大学 | Anti-yellowing titanium dioxide/fatty acid-based leather fatliquoring agent and preparation method thereof |
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