CN108193003B - Preparation method of multifunctional metal-containing organic phosphorus tanning agent - Google Patents
Preparation method of multifunctional metal-containing organic phosphorus tanning agent Download PDFInfo
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- CN108193003B CN108193003B CN201711473948.9A CN201711473948A CN108193003B CN 108193003 B CN108193003 B CN 108193003B CN 201711473948 A CN201711473948 A CN 201711473948A CN 108193003 B CN108193003 B CN 108193003B
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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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
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Abstract
The invention discloses a preparation method of a metal-containing multifunctional organic phosphorus tanning agent, belonging to the field of leather chemical industry. The present invention uses p-aminobenzoic acid and tetra-hydroxymethyl quaternary phosphonium salt to react, and then adds metal salt solution to prepare the organophosphorus tanning agent containing aluminium, chromium, zirconium or iron metal. Compared with the common organic phosphorus tanning agent retanned chromium leather, the metal-containing organic phosphorus tanning agent retanned chromium leather obtained by the invention has the advantages that the finished leather is white, the grain surface is fine, the shrinkage temperature, the physical and mechanical properties and the like are improved, and particularly the tearing strength and the tensile strength are obviously improved; endows the finished leather with good water resistance and low formaldehyde performance. In addition, the synthesized metal-containing organophosphorus tanning agent has good selective filling effect and is beneficial to fatliquoring, so that the leather after retanning and fatliquoring is soft and plump, and multiple functions are endowed to the finished leather.
Description
Technical Field
The invention relates to the field of leather chemical industry, in particular to a preparation method of a metal-containing multifunctional organic phosphorus tanning agent.
Background
Tanning is a process of metamorphism which converts hides into leather, while chemical materials which can convert skins into leather are called tanning agents, and among the tanning agents which can be used in the process of leather production are inorganic tanning agents, organic tanning agents and the like.
In recent years, tetrakis hydroxymethyl phosphonium salts have attracted attention as organic phosphorus tanning agents. The organic phosphorus tanning agent not only has stronger crosslinking capability with leather glue, but also can endow finished leather with performances of corrosion resistance, flame retardance, stronger tearing strength and the like.
However, because four hydroxymethyl groups are arranged around one phosphorus atom in the molecular structure of the organophosphorus tanning agent and cannot completely react with collagen, the remaining hydroxymethyl groups are converted and release formaldehyde, so that the content of free formaldehyde in finished leather can be increased.
In addition, the leather grain surface tanned by the organophosphorus tanning agent is white, but is flat, thin and not full enough.
Disclosure of Invention
In order to make up the defects of the prior art and solve the problems that the leather obtained after the treatment of the organic phosphorus tanning agent in the prior art has high free formaldehyde content, is relatively flat and thin and has insufficient fullness, the invention provides a preparation method of a metal-containing multifunctional organic phosphorus tanning agent. The obtained leather is white, the grain surface is fine, the shrinkage temperature, the physical and mechanical properties and the like are improved, and particularly, the tearing strength and the tensile strength are obviously improved; endows the finished leather with good water resistance and low formaldehyde performance.
The technical scheme of the invention is as follows:
a preparation method of a multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
1) dissolving p-aminobenzoic acid in an alkaline solution;
2) dripping the solution obtained in the step 1) into tetrakis hydroxymethyl phosphonium salt, and stirring and mixing;
3) adjusting the pH value to 6.0-9.0, and reacting for 1-3 hours at the temperature of 25-55 ℃;
4) adjusting the pH value to 1.5-3.0, dripping a metal salt solution of aluminum, chromium, zirconium and iron into the reaction solution obtained in the step 3), and reacting for 1-3 hours at normal temperature to obtain the metal-containing multifunctional organic phosphorus tanning agent.
The chemical formula of the multifunctional metal-containing organophosphorus tanning agent obtained by the invention is as follows:
preferably, the molar ratio of the p-aminobenzoic acid, the tetrakis (hydroxymethyl) phosphonium sulfate and the metal salt is 0.2-0.6:0.7-2.0: 0.7-2.0.
Preferably, the alkaline solution in step 1) is a sodium formate solution and/or a sodium acetate solution.
Preferably, the tetrakis hydroxymethyl phosphonium salt in step 2) is tetrakis hydroxymethyl phosphonium sulfate or tetrakis hydroxymethyl phosphonium chloride.
Preferably, sodium formate and/or sodium acetate is used to adjust the pH in step 3).
Preferably, the pH is adjusted in step 4) with an organic acid.
Further, the organic acid is formic acid and/or acetic acid.
Preferably, the metal salt solution in step 4) is a sulfate salt solution or a chloride salt solution of aluminum, chromium, zirconium and iron.
The invention has the beneficial effects that:
compared with the common organic phosphorus tanning agent retanned chromium leather, the retanned chromium leather containing the metal-containing organic phosphorus tanning agent has the advantages that the finished leather is white, the grain surface is fine, the shrinkage temperature, the physical and mechanical properties and the like are improved, and particularly the tearing strength and the tensile strength are obviously improved; endows the finished leather with good water resistance and low formaldehyde performance.
In addition, the synthesized metal-containing organic phosphorus tanning agent has good filling and selective filling effects, and the thickness of leather is increased and the position difference is reduced. The synthesized metal-containing organophosphorus tanning agent is beneficial to the effect of fatliquoring, so that the leather after retanning and fatliquoring is soft and plump, and multiple functions are endowed to the finished leather.
Detailed Description
Example 1:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.3 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.0 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 7.0 by using a sodium formate solution (diluted by 1: 10), controlling the temperature at 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 1.5 with a formic acid solution (1: 10 dilution), and 1.0 mol of aluminum sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
The leather tanned by the metal-containing multifunctional organophosphorus tanning agent obtained in the embodiment has fine grain surface, soft leather body and white appearance, the tearing strength is improved by 15-18% compared with that of the unmodified organophosphorus tanning agent, the tensile strength is improved by about 20-30%, the filling and selective filling effects are obvious, the thickness of the leather is increased, and the position difference is reduced.
Example 2:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.3 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.0 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 8.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 35 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 3.0 with a formic acid solution (1: 10 dilution), 1.0 mol of chromium sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, and the reaction was carried out at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
The leather tanned by the metal-containing multifunctional organophosphorus tanning agent obtained in the embodiment has fine grain surface, soft leather body and white appearance, the tearing strength is improved by 12-15% compared with that of the unmodified organophosphorus tanning agent, the tensile strength is improved by about 20-30%, the filling and selective filling effects are obvious, the thickness of the leather is increased, and the position difference is reduced.
Example 3:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.45 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.5 mol of tetrakis (hydroxymethyl) phosphonium chloride with accurately weighed mass concentration according to 100%, and the mixture is stirred continuously to be mixed.
(3) Adjusting the pH value to 6.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.5 with a formic acid solution (1: 10 dilution), and 1.5 mol of aluminum sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
The leather tanned by the metal-containing multifunctional organophosphorus tanning agent obtained in the embodiment has fine grain surface, soft leather body and white appearance, the tearing strength is improved by 16-20% compared with that of the unmodified organophosphorus tanning agent, the tensile strength is improved by about 20-30%, the filling and selective filling effects are obvious, the thickness of the leather is increased, and the position difference is reduced.
Example 4:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.3 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.0 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 9.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.0 with a formic acid solution (1: 10 dilution), 1.5 mol of zirconium sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, and the reaction was carried out at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
The leather tanned by the metal-containing multifunctional organophosphorus tanning agent obtained in the embodiment has fine grain surface, soft leather body and white appearance, the tearing strength is improved by 15-18% compared with that of the unmodified organophosphorus tanning agent, the tensile strength is improved by about 20-30%, the filling and selective filling effects are obvious, the thickness of the leather is increased, and the position difference is reduced.
Example 5:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.3 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.0 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 7.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.0 with a formic acid solution (1: 10 dilution), 1.5 mol of iron sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, and the reaction was carried out at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
The leather tanned by the metal-containing multifunctional organophosphorus tanning agent obtained in the embodiment has fine grain surface, soft leather body and white appearance, the tearing strength is improved by 15-18% compared with that of the unmodified organophosphorus tanning agent, the tensile strength is improved by about 20-30%, the filling and selective filling effects are obvious, the thickness of the leather is increased, and the position difference is reduced.
Example 6:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.3 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.0 mol of tetrakis (hydroxymethyl) phosphonium chloride which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 7.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 1.5 with a formic acid solution (1: 10 dilution), and 0.75 mol of aluminum sulfate, accurately weighed in mass concentration as 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 7:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.4 mol of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.2 mol of tetrakis hydroxymethyl phosphonium sulfate with accurately weighed mass concentration according to 100%, and the mixture is stirred continuously to be mixed.
(3) Adjusting the pH value to 7.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 55 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.0 with a formic acid solution (1: 10 dilution), and 1.2 mol of aluminum sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 8:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.6 mol of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 2.0 mol of tetrakis (hydroxymethyl) phosphonium chloride with accurately weighed mass concentration according to 100%, and the mixture is stirred continuously to be mixed.
(3) Adjusting the pH value to 6.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 55 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.5 with a formic acid solution (1: 10 dilution), 2.0 mol of chromium sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, and the reaction was carried out at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 9:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.6 mol of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 2.0 mol of tetrakis (hydroxymethyl) phosphonium chloride with accurately weighed mass concentration according to 100%, and the mixture is stirred continuously to be mixed.
(3) Adjusting the pH value to 7.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.0 with a formic acid solution (1: 10 dilution), and 2.0 mol of zirconium sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 10:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.6 mol of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 2.0 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 8.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.0 with a formic acid solution (1: 10 dilution), and 2.0 mol of aluminum sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 11:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.48 mol of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.6 mol of tetrakis hydroxymethyl phosphonium sulfate with accurately weighed mass concentration according to 100%, and the mixture is stirred continuously to be mixed.
(3) Adjusting the pH value to 7.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 45 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.0 with a formic acid solution (1: 10 dilution), and 1.6 mol of aluminum sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 12:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.3 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.0 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 7.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 25 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.5 with a formic acid solution (1: 10 dilution), 1.0 mol of chromium sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, and the reaction was carried out at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 13:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.3 mole of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 1.0 mol of tetrakis (hydroxymethyl) phosphonium chloride which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 8.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 25 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.5 with a formic acid solution (1: 10 dilution), and 1.0 mol of aluminum sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, followed by reaction at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 14:
(1) accurately weighed 0.2 mol of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 0.7 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 9.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 25 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.0 with a formic acid solution (1: 10 dilution), 0.7 mol of aluminum sulfate having a mass concentration of 100% was dissolved in water and added dropwise, and the reaction was carried out at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
Example 15:
the preparation method of the multifunctional metal-containing organophosphorus tanning agent comprises the following steps:
(1) accurately weighed 0.2 mol of p-aminobenzoic acid with a mass concentration of 100% was dissolved in an alkaline solution.
(2) Then the p-aminobenzoic acid solution is added dropwise into 0.7 mol of tetrakis hydroxymethyl phosphonium sulfate which is accurately weighed and has a mass concentration of 100%, and the mixture is continuously stirred and mixed.
(3) Adjusting the pH value to 6.0 by using an alkaline solution (diluted by 1: 10), controlling the temperature to be 25 ℃, and carrying out heat preservation reaction for 2 hours;
(4) then, the pH was adjusted to 2.5 with a formic acid solution (1: 10 dilution), and 0.7 mol of ferric sulfate, accurately weighed at a mass concentration of 100%, was dissolved in water and added dropwise, and the reaction was carried out at room temperature for 2 hours. And (3) after the reaction is finished, obtaining the metal-containing multifunctional organophosphorus tanning agent.
In the above examples, the Tetrakis Hydroxymethyl Phosphonium Sulfate (THPS) or tetrakis hydroxymethyl phosphonium chloride (hci) in the mass concentration of 100% means pure Tetrakis Hydroxymethyl Phosphonium Sulfate (THPS) or tetrakis hydroxymethyl phosphonium chloride (hci) not doped with any impurities, and if the Tetrakis Hydroxymethyl Phosphonium Sulfate (THPS) or tetrakis hydroxymethyl phosphonium chloride (hci) is not one hundred percent pure, it should be converted to one hundred percent pure tetrakis hydroxymethyl phosphonium sulfate or tetrakis hydroxymethyl phosphonium chloride (hci) when added.
In the above-described examples, the p-aminobenzoic acid whose mass concentration is 100% means pure p-aminobenzoic acid not doped with any impurities, and if the p-aminobenzoic acid is not one hundred percent pure, it should be converted into one hundred percent pure p-aminobenzoic acid when added.
In the above examples, the aluminum sulfate or chromium sulfate or zirconium sulfate or iron sulfate at the mass concentration of 100% refers to pure aluminum sulfate or chromium sulfate or zirconium sulfate or iron sulfate, if they are not one hundred percent pure, and when they are added, they should be converted to one hundred percent pure aluminum sulfate or chromium sulfate or zirconium sulfate or iron sulfate.
Claims (8)
1. The preparation method of the metal-containing multifunctional organophosphorus tanning agent is characterized by comprising the following steps:
1) dissolving p-aminobenzoic acid in an alkaline solution;
2) dripping the solution obtained in the step 1) into tetrakis hydroxymethyl phosphonium salt, and stirring and mixing;
3) adjusting the pH value to 6.0-9.0, and reacting for 1-3 hours at the temperature of 25-55 ℃;
4) adjusting the pH value to 1.5-3.0, dripping a metal salt solution of aluminum, chromium, zirconium and iron into the reaction solution obtained in the step 3), and reacting for 1-3 hours at normal temperature to obtain the metal-containing multifunctional organic phosphorus tanning agent.
2. The method for preparing the multifunctional metal-containing organophosphorus tanning agent according to claim 1, wherein: the mol ratio of the para aminobenzoic acid, the tetra-hydroxymethyl quaternary phosphonium salt and the metal salt is 0.2-0.6:0.7-2.0: 0.7-2.0.
3. The method for preparing a multifunctional metal-containing organophosphorus tanning agent according to claim 1 or 2, wherein: the alkaline solution in the step 1) is a sodium formate solution and/or a sodium acetate solution.
4. The method for preparing a multifunctional metal-containing organophosphorus tanning agent according to claim 1 or 2, wherein: the tetrakis hydroxymethyl phosphonium salt in the step 2) is tetrakis hydroxymethyl phosphonium sulfate and tetrakis hydroxymethyl phosphonium chloride.
5. The method for preparing a multifunctional metal-containing organophosphorus tanning agent according to claim 1 or 2, wherein: in the step 3), sodium formate and/or sodium acetate are used for adjusting the pH value.
6. The method for preparing a multifunctional metal-containing organophosphorus tanning agent according to claim 1 or 2, wherein: and 4) adjusting the pH value by adopting organic acid in the step 4).
7. The method for preparing the multifunctional metal-containing organophosphorus tanning agent according to claim 6, wherein: the organic acid is formic acid and/or acetic acid.
8. The method for preparing the multifunctional metal-containing organophosphorus tanning agent according to claim 1, wherein: the metal salt solution in the step 4) is a sulfate solution or a chloride salt solution of aluminum, chromium, zirconium and iron.
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CN1760377A (en) * | 2005-11-04 | 2006-04-19 | 四川大学 | Composition of tanning agent containing modified tara mimosa extract, and bating method without chrome |
CN101314797A (en) * | 2008-07-15 | 2008-12-03 | 四川大学 | High-fire-retardancy aminoresin nano-complex-function tanning agent |
CN105154598A (en) * | 2015-08-24 | 2015-12-16 | 齐鲁工业大学 | Preparing method for modifying organophosphorus tanning agent through compound containing amidogen and carboxyl functional groups simultaneously |
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CN1760377A (en) * | 2005-11-04 | 2006-04-19 | 四川大学 | Composition of tanning agent containing modified tara mimosa extract, and bating method without chrome |
CN101314797A (en) * | 2008-07-15 | 2008-12-03 | 四川大学 | High-fire-retardancy aminoresin nano-complex-function tanning agent |
CN105154598A (en) * | 2015-08-24 | 2015-12-16 | 齐鲁工业大学 | Preparing method for modifying organophosphorus tanning agent through compound containing amidogen and carboxyl functional groups simultaneously |
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