CN109971898B - Zwitterionic non-metal tanning agent - Google Patents

Zwitterionic non-metal tanning agent Download PDF

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CN109971898B
CN109971898B CN201910284145.1A CN201910284145A CN109971898B CN 109971898 B CN109971898 B CN 109971898B CN 201910284145 A CN201910284145 A CN 201910284145A CN 109971898 B CN109971898 B CN 109971898B
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tanning agent
tanning
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metal
polyamine compound
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CN109971898A (en
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邹祥龙
任便利
沈晓军
柴玉叶
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Wenzhou University
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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
    • 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
    • C14C3/26—Chemical tanning by organic agents using other organic substances, containing halogen

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Abstract

The invention discloses a zwitterionic non-metal tanning agent, which is prepared by adding a certain amount of polyamine compound and chloroacetic acid into a reactor, adjusting the pH of a reaction solution to 10-12 by using an alkaline substance, carrying out heat preservation reaction at 70-80 ℃ for 3-4 h, then cooling to room temperature, adding a certain amount of acetone, cooling to control the temperature to 0-5 ℃, adding a certain amount of cyanuric chloride, adjusting the pH to 6.0-7.0 by using an alkaline substance solution, and carrying out reaction for 3-4 h. And (3) decompressing and steaming out the acetone at the temperature of 10-20 ℃ to obtain the zwitterionic non-metal tanning agent. The zwitterionic non-metal tanning agent prepared by the invention has the characteristics of amphiprotic property, good tanning property, white and flat leather surface and good compatibility with anionic materials.

Description

Zwitterionic non-metal tanning agent
Technical Field
The invention relates to the technical field of leather chemical synthesis, in particular to a zwitterion non-metal tanning agent and a preparation method thereof.
Background
Tanning agents are the key process step for changing leather into leather in the tanning process, and the tanning method has a decisive influence on the performance and quality of leather products. Among the various tanning agents known in the art (i.e. mineral tanning agents, vegetable tanning agents, aldehyde tanning agents, synthetic tanning agents, etc.), chrome tanning agents are most widely used, are suitable for the production of different kinds of leather products, and provide satisfactory product properties (such as high shrinkage temperature, good leather sensory and physico-mechanical properties and good compatibility with leather specific chemicals such as retanning agents, fatliquoring agents, dyes, etc.).
However, with the increase of environmental awareness, the limitations of chrome tanning agents become more obvious, such as limited chrome resources, and the chrome tanning waste liquid and the chrome-containing solid waste are not easy to treat. In addition, in the chrome tanning process, the actual utilization rate of the chrome tanning agent is 60-70%, the chrome content in the tanned waste liquid is high, the sewage treatment is difficult to reach the standard, and trivalent chromium in leather and sewage can be converted into carcinogenic hexavalent chromium under certain conditions, so that great harm is caused to the environment. Therefore, the development of the non-chrome tanning agent with excellent performance and the tanning method thereof is the key for fundamentally solving the problem of chrome pollution and realizing the sustainable development of tanning, and related researches are also the focus and the key points of attention in the current tanning field.
In the existing chrome-free tanning methods, such as zirconium tanning, aluminum tanning, vegetable tanning, organic tanning agent tanning, various combined tanning methods and the like, wherein the vegetable tanning agent and the organic tanning agent (aldehyde tanning agent, organic phosphine tanning agent and organic chlorine tanning agent) are widely applied, but a remarkable gap exists in the comprehensive performance compared with chrome tanning agents. The vegetable tanning agent is compact in tanning, good in formability, but poor in extensibility, low in tanning shrinkage temperature and not suitable for being used as a main tanning agent for light leather. The tanning with aldehyde tanning agent and organic phosphine tanning agent has the problem of excessive formaldehyde. In addition, compared with a chrome tanning agent, the isoelectric point of leather tanned by the non-metal tanning agent is lower, for example, the isoelectric point of glutaraldehyde tanned leather is 5.1-5.2, and the isoelectric point of vegetable tanned leather is about 4.0, which are both obviously lower than the isoelectric point (7.7-7.9) of chrome tanned leather, so that the surfaces of the aldehyde tanned leather and the vegetable tanned leather are negatively or weakly cationic, and the binding capacity of the aldehyde tanned leather and anion materials such as retanning agents, fatliquoring agents and dyes in leather making is weak. Generally, aldehyde tanning and organic chloride tanning still need to adopt a certain amount of chrome tanning agent for retanning so as to improve the absorption of anion materials such as the retanning agent, a fatting agent, dye and the like, so that the pollution problem existing in chrome tanning is still difficult to solve substantially by the prior non-metal tanning agent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a zwitterion non-metal tanning agent and a preparation method thereof; the tanning agent has good compatibility with an anion material special for tanning, has good tanning property, and has white, flat and fine leather surface and high absorptivity of the tanning to the anion material; meanwhile, the pollution caused by the method is very small, and the method is very environment-friendly.
In order to achieve the purpose, the invention provides the following technical scheme: a zwitterionic non-metal tanning agent has a molecular structural formula
Figure GDA0003034791070000021
Wherein n is between 1 and 10;
R1 、R2 、R3 and R4 is-H or-CH2COOM or
Figure GDA0003034791070000022
Wherein R is1 、R2 、R3 And R4 In which at least one group is
Figure GDA0003034791070000023
And at least one group is-CH2COOM, M represents hydrogen or an alkali metal ion.
As a further improvement of the invention, the tanning agent is prepared by reacting polyamine compound, chloroacetic acid and cyanuric chloride;
the molecular structural formula of the polyamine compound is shown in the specification
Figure GDA0003034791070000031
n is 1 to 10.
As a further improvement of the present invention, the polyamine compound is any one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.
As a further improvement of the invention, the preparation method of the zwitterionic non-metal tanning agent comprises the following steps:
step 1: sequentially adding deionized water, a polyamine compound and chloroacetic acid into a reactor to form reaction liquid; then heating to 70-80 ℃, adjusting the pH of the reaction solution by using an alkaline substance water solution with the mass concentration of 10-25% to ensure that the pH of the reaction solution is 10-12, and then carrying out heat preservation reaction for 3-4 h;
step 2: cooling the reaction liquid obtained in the step 1 to room temperature, adding acetone, cooling, controlling the temperature to be 0-5 ℃, then adding cyanuric chloride into the reactor, dropwise adding an alkaline substance aqueous solution with the mass concentration of 10-25% to adjust the pH of the reaction system, enabling the pH of the reaction system to be 5.5-6.5, and reacting for 3-6 hours;
and step 3: and after the reaction is finished, decompressing and steaming out the acetone at the temperature of 10-20 ℃ to obtain the zwitterion non-metal tanning agent.
As a further improvement of the present invention, the ratio of the amount of chloroacetic acid species to the amount of hydrogen species contained in the amine groups in the molecule of the polyamine compound in step 1 is 0.3 to 0.7.
As a further improvement of the method, the mass of the deionized water in the step 1 accounts for 50-70% of the total mass of the reaction liquid.
As a further improvement of the invention, the alkaline substance in the step 1 and the step 2 is any one of sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
As a further improvement of the invention, the ratio of the mass of the acetone in the step 2 to the mass of the deionized water in the step 1 is 1: 1.
As a further improvement of the invention, the amount of the cyanuric chloride substance in the step 2 is the difference between the amount of the hydrogen substance contained in the amine group in the polyamine compound in the step 1 and the amount of the chloroacetic acid substance.
The invention has the beneficial effects that:
1. the product does not contain harmful substances such as heavy metal, phenol, formaldehyde and the like.
2. The tanning agent contains a plurality of active-Cl groups, can react with primary amino and secondary amino in skin collagen to generate tanning property, and the tanning shrinkage temperature can reach 78-83 ℃. The pH value at the initial stage of tanning is 7.0-9.0, and the pH value can be kept at 5-6 after the tanning is finished. Compared with chrome tanning, the raw hide does not need pickling process, and salt pollution caused by pickling process can be eliminated.
3. The tanning agent is amphoteric and contains anionic carboxyl group and cationic tertiary amino group. Under alkaline conditions, the tanning agent is electronegative, has good permeability in leather, and can form chemical crosslinking action with collagen fibers to show good tanning property. Under the acidic condition, the carboxyl is uncharged, the tertiary amine group obtains a proton and has electropositivity, and the combination of the collagen fiber to anionic materials such as a fatting agent, a retanning agent and a dye can be improved. Therefore, compared with synthetic tanning agents such as vegetable tanning agents, aldehyde tanning agents and the like, the tanning agent has better compatibility with anion materials special for tanning such as retanning agents, fatliquoring agents, dyes and the like.
Drawings
FIG. 1 is a schematic diagram of a synthetic chemical reaction of a zwitterionic non-metal tanning agent prepared in example 2 of the present invention;
FIG. 2 is a schematic representation of zwitterionic non-metal tanning;
FIG. 3 is an infrared spectrum of the product of the reaction of diethylenetriamine with chloroacetic acid according to the present invention;
FIG. 4 is an infrared spectrum of the zwitterionic non-metallic tanning agent prepared in example 2 of the present invention;
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
A preparation method of a zwitterionic non-metal tanning agent specifically comprises the following steps:
(1) adding 37.2g of deionized water, 0.1mol of ethylenediamine and 0.2mol of chloroacetic acid into a reactor, heating to 75 ℃, adjusting the pH value to 10-12 by using a sodium hydroxide aqueous solution with the mass concentration of 20%, and carrying out heat preservation reaction for 4 hours.
(2) And (2) cooling the reactant in the step (1) to room temperature, adding 37.2g of acetone, cooling in an ice-water bath, controlling the temperature of the reaction liquid to be 0-5 ℃, then adding 18.4g of cyanuric chloride, adjusting the pH of the reaction liquid to be 6.0-7.0 by using a sodium carbonate solution with the mass concentration of 20%, and reacting for 3-6 h.
(3) And (3) distilling the reaction liquid obtained in the step (2) at 10-20 ℃ under reduced pressure to remove the solvent acetone, thus obtaining the zwitterion non-metal tanning agent.
Example 2
A preparation method of a zwitterionic non-metal tanning agent specifically comprises the following steps:
(1) adding 57.75g of deionized water, 0.1mol of diethylenetriamine and 0.3mol of chloroacetic acid into a reactor, heating to 75 ℃, adjusting the pH value to 10-12 by using a sodium hydroxide aqueous solution with the mass concentration of 20%, and carrying out heat preservation reaction for 4 hours.
(2) And (2) cooling the reactant in the step (1) to room temperature, adding 57.75g of acetone, cooling in an ice-water bath, controlling the temperature of the reaction liquid to be 0-5 ℃, then adding 36.8g of cyanuric chloride, adjusting the pH of the reaction liquid to be 6.0-7.0 by using a sodium carbonate solution with the mass concentration of 20%, and reacting for 3-6 h.
(3) And (3) distilling the reaction liquid obtained in the step (2) at 10-20 ℃ under reduced pressure to remove the solvent acetone, thus obtaining the zwitterion non-metal tanning agent.
Example 3
A preparation method of a zwitterionic non-metal tanning agent specifically comprises the following steps:
(1) adding 78.3g of deionized water, 0.1mol of triethylene tetramine and 0.4mol of chloroacetic acid into a reactor, heating to 75 ℃, adjusting the pH value to 10-12 by using a sodium hydroxide aqueous solution with the mass concentration of 20%, and carrying out heat preservation reaction for 4 hours.
(2) And (2) cooling the reactant in the step (1) to room temperature, adding 78.3g of acetone, cooling in an ice-water bath, controlling the temperature of the reaction liquid to be 0-5 ℃, then adding 36.8g of cyanuric chloride, adjusting the pH of the reaction liquid to be 6.0-7.0 by using a sodium carbonate solution with the mass concentration of 20%, and reacting for 3-6 h.
(3) And (3) distilling the reaction liquid obtained in the step (2) at 10-20 ℃ under reduced pressure to remove the solvent acetone, thus obtaining the zwitterion non-metal tanning agent.
Example 4
A preparation method of a zwitterionic non-metal tanning agent specifically comprises the following steps:
(1) adding 98.85g of deionized water, 0.1mol of tetraethylenepentamine and 0.5mol of chloroacetic acid into a reactor, heating to 75 ℃, adjusting the pH value to 10-12 by using a sodium hydroxide aqueous solution with the mass concentration of 20%, and carrying out heat preservation reaction for 4 hours.
(2) And (2) cooling the reactant in the step (1) to room temperature, adding 98.85g of acetone, cooling in an ice-water bath, controlling the temperature of the reaction liquid to be 0-5 ℃, then adding 36.8g of cyanuric chloride, adjusting the pH of the reaction liquid to be 6.0-7.0 by using a sodium carbonate solution with the mass concentration of 20%, and reacting for 3-6 h.
(3) And (3) distilling the reaction liquid obtained in the step (2) at 10-20 ℃ under reduced pressure to remove the solvent acetone, thus obtaining the zwitterion non-metal tanning agent.
Example 5
A preparation method of a zwitterionic non-metal tanning agent specifically comprises the following steps:
(1) adding 119.4g of deionized water, 0.1mol of pentaethylenehexamine and 0.6mol of chloroacetic acid into a reactor, heating to 75 ℃, adjusting the pH value to 10-12 by using a sodium hydroxide aqueous solution with the mass concentration of 20%, and carrying out heat preservation reaction for 4 hours.
(2) And (2) cooling the reactant in the step (1) to room temperature, adding 119.4g of acetone, cooling in an ice-water bath, controlling the temperature of the reaction liquid to be 0-5 ℃, then adding 36.8g of cyanuric chloride, adjusting the pH of the reaction liquid to be 6.0-7.0 by using a sodium carbonate solution with the mass concentration of 20%, and reacting for 3-6 h.
(3) And (3) distilling the reaction liquid obtained in the step (2) at 10-20 ℃ under reduced pressure to remove the solvent acetone, thus obtaining the zwitterion non-metal tanning agent.
Application examples
The properties of the tanning agents of examples 1 to 5 were investigated using sheep hide as experimental skin and Granofin Easy F-90, an active chlorine organic tanning agent from stahl as a control sample.
TABLE 1 tanning oiling process (sheep acid leather weighing by squeezing water, and weight gain three times as the basis for the use amount of each material in the table)
Figure GDA0003034791070000071
TABLE 2 evaluation results of wet heat shrinkage temperature and softness of tanned leather
Figure GDA0003034791070000072
Figure GDA0003034791070000081
Remarking: dry leather softness was rated by an experienced tannery in five grades
As can be seen from Table 2, the zwitterionic non-metallic tanning agents of the invention all show better tanning properties than hides (wet heat shrinkage temperature about 60℃.), and are preferred in examples 4 and 5. Compared with a control sample F-90, the tanning agent is a zwitterionic non-metal tanning agent, has the amphoteric characteristic, is electropositive under the condition of lower pH, can introduce a certain amount of cationic groups on the surface of leather fibers after tanning, and enhances the absorption of the leather fibers on the anionic material fatliquor. F-90 tanned leather is electronegative, and has weak binding capacity to an anionic fatting agent, so that waste liquid is turbid, and the tanned leather has poor softness. In the embodiments 1 to 5 of the zwitterionic non-metal tanning agent, the number of the tertiary amine groups contained in the molecules of the tanning agent is increased, the positive electricity of corresponding tanning fibers is enhanced, and the absorptivity of the fatting agent is gradually increased, so that the waste liquid is changed from turbid to clear, and the softness of fatted leather is gradually enhanced.
Chemical reaction schematic formula for synthesis of zwitterionic non-metal tanning agent (polyamine compound takes diethylenetriamine as an example):
Figure GDA0003034791070000082
FIG. 1 is a schematic diagram of the synthesis of a zwitterionic non-metallic tanning agent;
FIG. 2 isA zwitterionic non-metal tanning scheme;
under neutral or alkalescent conditions, the surface of the collagen fiber is electronegative, carboxyl of a zwitter-ion non-metal tanning agent (hereinafter referred to as tanning agent) is negatively charged, the binding capacity with the fiber is weak, the permeability in leather is good, and active chlorine on molecules of the tanning agent can react with amino on the collagen fiber to form chemical crosslinking among the fibers, so that the tanning effect is achieved. When the pH value is reduced to 3.8-4.0, a proton obtained from the carboxyl group is uncharged, and a proton obtained from the tertiary amine group is electropositive, so that the electropositive property of the surface of the collagen fiber can be enhanced, and the binding capacity of the leather to an anion material is improved. The schematic diagram of tanning process and electrical change is shown in FIG. 2: (
Figure GDA0003034791070000091
Indicating collagen fibers).
Figure GDA0003034791070000092
FIG. 3 is an infrared spectrum of the product of the reaction of diethylenetriamine with chloroacetic acid according to the present invention;
3300cm is clear from FIG. 3-1The absorption peaks are superposed by O-H and N-H stretching vibration; 1725cm-1C ═ O vibration characteristic absorption peak on carboxyl; 1652cm-1Is an N-H bending vibration absorption peak; 1250-1050 cm-1The band is C-N stretching vibration absorption peak. The product has the purpose of spectrum analysisStructural features of the target product.
FIG. 4 is an infrared spectrum of the zwitterionic non-metallic tanning agent prepared in example 2;
as can be seen from FIG. 4, 3300cm-1Is an O-H stretching vibration absorption peak; 1715cm-1C ═ O vibration characteristic absorption peak on carboxyl; 1615. 1443 and 1404cm-1Is a characteristic absorption peak of the triazine ring; 1100-1050 cm-1Is a C-N stretching vibration absorption peak. 1652cm, compared with FIG. 3-1The N-H bending vibration absorption peak disappears, and a characteristic absorption peak of triazine ring newly appears, which indicates that MAT reacts with cyanuric chloride to obtain a target product.
Compared with the prior art, the invention has the following advantages:
1) the product does not contain harmful substances such as heavy metal, phenol, formaldehyde and the like.
2) The tanning agent contains a plurality of active-Cl groups, can react with primary amino and secondary amino in skin collagen to generate tanning property, and the tanning shrinkage temperature can reach 78-83 ℃. The pH value at the initial stage of tanning is 7.0-9.0, and the pH value can be kept at 5-6 after the tanning is finished. Compared with chrome tanning, the raw hide does not need pickling process, and salt pollution caused by pickling process can be eliminated.
3) The tanning agent is amphoteric and contains anionic carboxyl group and cationic tertiary amino group. Under alkaline conditions, the tanning agent is electronegative, has good permeability in leather, and can form chemical crosslinking action with collagen fibers to show good tanning property. Under the acidic condition, the carboxyl is uncharged, the tertiary amine group obtains a proton and has electropositivity, and the combination of the collagen fiber to anionic materials such as a fatting agent, a retanning agent and a dye can be improved. Therefore, compared with synthetic tanning agents such as vegetable tanning agents, aldehyde tanning agents and the like, the tanning agent has better compatibility with anion materials special for tanning such as retanning agents, fatliquoring agents, dyes and the like.
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 (6)

1. A zwitterionic non-metallic tanning agent is characterized in that: the molecular structural formula of the tanning agent is
Figure FDA0003034791060000011
Wherein n is between 1 and 10;
R1 、R2 、R3 and R4 is-H or-CH2COOM or
Figure FDA0003034791060000012
Wherein R is1 、R2 、R3 And R4 In which at least one group is
Figure FDA0003034791060000013
And at least one group is-CH2COOM, M represents hydrogen or an alkali metal ion;
the tanning agent is prepared by reacting polyamine compound, chloroacetic acid and cyanuric chloride;
the molecular structural formula of the polyamine compound is shown in the specification
Figure FDA0003034791060000014
n is 1-10;
the polyamine compound is any one or a mixture of ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine;
the preparation method comprises the following steps:
the method comprises the following steps:
step 1: sequentially adding deionized water, a polyamine compound and chloroacetic acid into a reactor to form reaction liquid; then heating to 70-80 ℃, adjusting the pH of the reaction solution by using an alkaline substance water solution with the mass concentration of 10-25% to ensure that the pH of the reaction solution is 10-12, and then carrying out heat preservation reaction for 3-4 h;
step 2: cooling the reaction liquid obtained in the step 1 to room temperature, adding acetone, cooling, controlling the temperature to be 0-5 ℃, then adding cyanuric chloride into the reactor, dropwise adding an alkaline substance aqueous solution with the mass concentration of 10-25% to adjust the pH of the reaction system, enabling the pH of the reaction system to be 5.5-6.5, and reacting for 3-6 hours;
and step 3: and after the reaction is finished, decompressing and steaming out the acetone at the temperature of 10-20 ℃ to obtain the zwitterion non-metal tanning agent.
2. A zwitterionic non-metal tanning agent according to claim 1, characterised in that: the ratio of the amount of chloroacetic acid species to the amount of hydrogen species contained in the amine groups in the molecule of the polyamine compound in step 1 is 0.3 to 0.7.
3. A zwitterionic non-metal tanning agent according to claim 2, characterised in that: in the step 1, the mass of the deionized water accounts for 50-70% of the total mass of the reaction liquid.
4. A zwitterionic non-metal tanning agent according to claim 3, characterized in that: the alkaline substance in the steps 1 and 2 is any one of sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
5. A zwitterionic non-metal tanning agent according to claim 4, characterized in that: the mass ratio of the acetone in the step 2 to the deionized water in the step 1 is 1: 1.
6. A zwitterionic non-metal tanning agent according to claim 5, characterized in that: the amount of cyanuric chloride in step 2 is the difference between the amount of hydrogen contained in the amine group in the polyamine compound in step 1 and the amount of chloroacetic acid.
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CN1165864A (en) * 1996-03-11 1997-11-26 罗姆和哈斯公司 Method of treating leather with amphoteric polymers
CN101343254A (en) * 2008-07-09 2009-01-14 中北大学 Gemini surfactant containing triazine ring
CN102250029A (en) * 2011-05-16 2011-11-23 修建东 Preparation method of triazine hydroxyethyl ethylenediamine polycarboxylic acid
CN108085434A (en) * 2017-12-29 2018-05-29 温州大学 A kind of leather organic tanning agent and preparation method thereof

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MX2012014190A (en) * 2010-10-28 2013-02-07 Clariant Finance Bvi Ltd Non-metal tanning process.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1165864A (en) * 1996-03-11 1997-11-26 罗姆和哈斯公司 Method of treating leather with amphoteric polymers
CN101343254A (en) * 2008-07-09 2009-01-14 中北大学 Gemini surfactant containing triazine ring
CN102250029A (en) * 2011-05-16 2011-11-23 修建东 Preparation method of triazine hydroxyethyl ethylenediamine polycarboxylic acid
CN108085434A (en) * 2017-12-29 2018-05-29 温州大学 A kind of leather organic tanning agent and preparation method thereof

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