CN114164308A - Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof - Google Patents
Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof Download PDFInfo
- Publication number
- CN114164308A CN114164308A CN202111366239.7A CN202111366239A CN114164308A CN 114164308 A CN114164308 A CN 114164308A CN 202111366239 A CN202111366239 A CN 202111366239A CN 114164308 A CN114164308 A CN 114164308A
- Authority
- CN
- China
- Prior art keywords
- hydrotalcite
- tanning agent
- metal complex
- self
- preparation
- 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
- 230000000694 effects Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 65
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 65
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 30
- 239000002114 nanocomposite Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 24
- 150000004696 coordination complex Chemical class 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 16
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 16
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 16
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 15
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004043 dyeing Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 125000000129 anionic group Chemical group 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a multi-carboxyl metal complex tanning agent with self-masking effect and a preparation method thereof. The complex tanning agent can be used for chrome-free tanning of leather, avoids the use of heavy metal chromium, ensures that the shrinkage temperature of the obtained finished leather can reach more than 90 ℃, all performances can reach the industrial standard, and promotes the absorption and utilization of anionic dyeing and finishing chemicals such as dye, fatting agent and the like by introducing the hydrotalcite with positive charge.
Description
Technical Field
The invention belongs to the field of leather chemicals, and relates to a multi-carboxyl metal complex tanning agent with a self-masking effect and a preparation method thereof.
Background
In recent years, the development of environment-friendly chrome-free tanning materials has become a main way for solving the problem of environmental pollution of the traditional chrome tanning method from the source, and the market demand of current consumers on high-added-value and high-quality chrome-free tanning products is met. Currently, chrome-free tanning agents mainly comprise two main classes of non-chrome metal tanning agents and organic tanning agents. Wherein the organic tanning agent mainly refers to plant polyphenol, aldehyde tanning agent, resin tanning agent, synthetic tanning agent, oil tanning agent and the like, and the non-chromium metal tanning agent mainly refers to zirconium tanning agent, aluminum tanning agent, titanium tanning agent, iron tanning agent and the like. However, the leather produced by the chrome-free tanning agent has the comprehensive quality which is not comparable with that of chrome-tanned leather. In recent years, non-chromium metal tanning agents are used in combination to realize advantage complementation, so that the defect of performance of a single non-chromium metal tanning agent is overcome, and the wide attention of researchers is paid. However, non-chrome metal tanning agents have poor alkali resistance, are easily crosslinked with collagen fibers on the surface in the tanning process, and have the phenomenon of surface over-tanning, so that the tanning performance is reduced. The defects of the non-chrome metal tanning agent can be properly improved by adding an organic ligand (namely a masking agent) with functional groups such as hydroxyl, carbonyl, carboxyl and the like into a tanning system.
Disclosure of Invention
The invention aims to provide a multi-carboxyl metal complex tanning agent with self-masking effect and a preparation method thereof aiming at the requirements of ecological tanning, the complex tanning agent can avoid the use of heavy metal chromium, the shrinkage temperature of the obtained finished leather can reach more than 90 ℃, all performances can reach the industrial standard, and the introduction of hydrotalcite with positive charge can promote the absorption and utilization of anionic dyeing and finishing chemicals such as dye, fatting agent and the like.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a multi-carboxyl metal complex tanning agent with a self-masking effect comprises the steps of firstly intercalating methacrylic acid and itaconic acid monomers into hydrotalcite layers by an ion exchange method, then initiating in-situ polymerization of the monomers to obtain a multi-carboxyl polymer/hydrotalcite nano composite material, and then mixing the multi-carboxyl polymer/hydrotalcite nano composite material with zirconium sulfate and aluminum sulfate to prepare the multi-carboxyl metal complex tanning agent with the self-masking effect.
The method specifically comprises the following steps of:
step one, preparing a polycarboxy polymer/hydrotalcite nano composite material:
weighing hydrotalcite, adding the hydrotalcite into water, and carrying out ultrasonic treatment for 0.5 h to obtain hydrotalcite dispersion liquid; mixing the hydrotalcite dispersion liquid, methacrylic acid, itaconic acid and water at the temperature of 60-85 ℃, stirring for 2 hours at 700 r/min, adding ammonium persulfate, sodium bisulfite and water, and stirring for 0.5 hour at 400 r/min; then adding methacrylic acid, itaconic acid, ammonium persulfate, sodium bisulfite and water, and stirring for 3 h to obtain a polycarboxy polymer/hydrotalcite nano composite material;
step two, preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate, and dissolving in 200-1000 parts of water to obtain a metal mixed solution;
step three, preparing a polycarboxyl metal complex tanning agent:
and adding the metal mixed solution into a polycarboxy polymer/hydrotalcite nano composite material, uniformly stirring, and spray-drying the obtained solution at the inlet temperature of 180 ℃ to obtain the polycarboxy metal complex tanning agent with the self-masking effect.
In the first step, the amount of hydrotalcite is 1-6% of the total mass of methacrylic acid and itaconic acid, wherein the total mass ratio of methacrylic acid to itaconic acid is 30: 15-90; the total ammonium persulfate dosage is 6-20% of the total mass of the methacrylic acid and the itaconic acid; the total sodium bisulfite dosage is 2-20% of the total mass of methacrylic acid and itaconic acid.
In the second step, the mass ratio of the zirconium sulfate to the aluminum sulfate is 3-40: 6-80.
In the third step, the mass ratio of the polycarboxy polymer/hydrotalcite nano composite material to the mixture of zirconium sulfate and aluminum sulfate is 0.5-5: 1.
The polycarboxyl metal complex tanning agent with self-masking effect prepared by any one of the preparation methods.
Compared with the prior art, the invention has the beneficial effects that:
the polycarboxyl polymer/hydrotalcite nano composite material is prepared by an in-situ polymerization method, and then is mixed with zirconium sulfate and aluminum sulfate in a certain proportion to prepare the polycarboxyl metal complex tanning agent with a self-masking effect. The compound tanning agent can be used for chrome-free tanning of leather, the use of heavy metal chromium is avoided, the shrinkage temperature of the obtained finished leather can reach more than 90 ℃, and all performances can reach the industrial standard; due to the permanent electropositivity of the hydrotalcite plate layer, the absorption and combination of anionic dyeing and finishing chemicals such as dye, fatting agent and the like in the later period of leather making are facilitated, so that the finished leather has good dyeing property and softness.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The implementation conditions used in the examples can be further adjusted according to the specific experimental environment, and the implementation conditions not mentioned are generally the conditions in routine experiments.
The polycarboxyl polymer/hydrotalcite nano composite material is prepared by an in-situ polymerization method, and then is mixed with zirconium sulfate and aluminum sulfate in a certain proportion to obtain the polycarboxyl metal complex tanning agent with a self-masking effect. The multi-carboxyl polymer containing rich carboxyl is utilized to improve the defect of surface over-tanning of the non-chromium metal tanning agent, the tanning performance is improved, and meanwhile, the permanent positive electricity of the hydrotalcite plate layer is utilized to promote the absorption and combination of anionic dyeing and finishing chemicals such as dye, fatting agent and the like in the later period of leather making, so that the finished leather has good dyeing performance and softness.
The preparation method of the multi-carboxyl metal complex tanning agent with the self-masking effect comprises the following steps of:
(1) preparation of polycarboxy polymer/hydrotalcite nanocomposite: weighing 0.45-7.2 parts of hydrotalcite, adding into 40 parts of water, and carrying out ultrasonic treatment for 0.5 h to obtain a hydrotalcite dispersion liquid; adding hydrotalcite dispersion liquid, 10 parts of methacrylic acid, 5-30 parts of itaconic acid and 10-60 parts of water into a three-neck flask at 60-85 ℃, stirring for 2 hours at 700 r/min, adding 0.9-8 parts of ammonium persulfate, 0.3-8 parts of sodium bisulfite and 33-102 parts of water, and stirring for 0.5 hour at 400 r/min; then adding 20 parts of methacrylic acid, 10-60 parts of itaconic acid, 1.8-16 parts of ammonium persulfate, 0.6-16 parts of sodium bisulfite and 86-324 parts of water, and stirring for 3 hours to obtain a polycarboxy polymer/hydrotalcite nano composite material;
(2) preparing a metal mixed solution: mixing zirconium sulfate and aluminum sulfate according to the ratio of (3-40) to (6-80), and dissolving in 200-1000 parts of water to obtain a metal mixed solution;
(3) preparing a polycarboxyl metal complex tanning agent: and adding the metal mixed solution into a certain amount of polycarboxy polymer/hydrotalcite nano composite material, uniformly stirring, and spray-drying the obtained solution at the inlet temperature of 180 ℃ to obtain the polycarboxy metal complex tanning agent with the self-masking effect.
Example 1:
(1) preparation of polycarboxy polymer/hydrotalcite nanocomposite:
weighing 5 parts of hydrotalcite, adding the hydrotalcite into 40 parts of water, and carrying out ultrasonic treatment for 0.5 h to obtain hydrotalcite dispersion liquid; adding hydrotalcite dispersion liquid, 10 parts of methacrylic acid, 20 parts of itaconic acid and 40 parts of water into a three-neck flask at 85 ℃, stirring for 2 hours at 700 r/min, adding 6 parts of ammonium persulfate, 6 parts of sodium bisulfite and 90 parts of water, stirring for 0.5 hour at 400 r/min, adding 20 parts of methacrylic acid, 40 parts of itaconic acid, 12 parts of ammonium persulfate, 12 parts of sodium bisulfite and 200 parts of water, and stirring for 3 hours to obtain a polycarboxy polymer/hydrotalcite nano composite material;
(2) preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate according to the proportion of 20:20, and dissolving in 500 parts of water to obtain a metal mixed solution;
(3) preparing a polycarboxyl metal complex tanning agent:
and adding the metal mixed solution into 3 parts of polycarboxy polymer/hydrotalcite nano composite material, uniformly stirring, and spray-drying the obtained solution at the inlet temperature of 180 ℃ to obtain the polycarboxy metal complex tanning agent with the self-masking effect.
Example 2:
(1) preparation of polycarboxy polymer/hydrotalcite nanocomposite:
weighing 2 parts of hydrotalcite, adding the hydrotalcite into 40 parts of water, and carrying out ultrasonic treatment for 0.5 h to obtain hydrotalcite dispersion liquid; adding a hydrotalcite dispersion liquid, 10 parts of methacrylic acid, 30 parts of itaconic acid and 60 parts of water into a three-neck flask at 75 ℃, stirring for 2 hours at 700 r/min, adding 8 parts of ammonium persulfate, 8 parts of sodium bisulfite and 102 parts of water, stirring for 0.5 hour at 400 r/min, adding 20 parts of methacrylic acid, 60 parts of itaconic acid, 16 parts of ammonium persulfate, 16 parts of sodium bisulfite and 324 parts of water, and stirring for 3 hours to obtain a polycarboxy polymer/hydrotalcite nano composite material;
(2) preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate according to the proportion of 30:10, and dissolving in 500 parts of water to obtain a metal mixed solution;
(3) preparing a polycarboxyl metal complex tanning agent:
and adding the metal mixed solution into 1 part of polycarboxy polymer/hydrotalcite nano composite material, uniformly stirring, and spray-drying the obtained solution at the inlet temperature of 180 ℃ to obtain the polycarboxy metal complex tanning agent with the self-masking effect.
Example 3:
(1) preparation of polycarboxy polymer/hydrotalcite nanocomposite:
weighing 6 parts of hydrotalcite, adding the hydrotalcite into 40 parts of water, and carrying out ultrasonic treatment for 0.5 h to obtain hydrotalcite dispersion liquid; adding a hydrotalcite dispersion liquid, 10 parts of methacrylic acid, 10 parts of itaconic acid and 30 parts of water into a three-neck flask at 60 ℃, stirring for 2 hours at 700 r/min, adding 4 parts of ammonium persulfate, 4 parts of sodium bisulfite and 80 parts of water, stirring for 0.5 hour at 400 r/min, adding 20 parts of methacrylic acid, 20 parts of itaconic acid, 8 parts of ammonium persulfate, 8 parts of sodium bisulfite and 240 parts of water, and stirring for 3 hours to obtain a polycarboxy polymer/hydrotalcite nano composite material;
(2) preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate according to the ratio of 40:10, and dissolving in 800 parts of water to obtain a metal mixed solution;
(3) preparing a polycarboxyl metal complex tanning agent:
and adding the metal mixed solution into 1.2 parts of polycarboxyl polymer/hydrotalcite nano composite material, uniformly stirring, and spray-drying the obtained solution at the inlet temperature of 180 ℃ to obtain the polycarboxyl metal complex tanning agent with the self-masking effect.
Example 4:
(1) preparation of polycarboxy polymer/hydrotalcite nanocomposite:
weighing 3 parts of hydrotalcite, adding the hydrotalcite into 40 parts of water, and carrying out ultrasonic treatment for 0.5 h to obtain hydrotalcite dispersion liquid; adding a hydrotalcite dispersion liquid, 10 parts of methacrylic acid, 20 parts of itaconic acid and 50 parts of water into a three-neck flask at 70 ℃, stirring for 2 hours at 700 r/min, adding 6 parts of ammonium persulfate, 4 parts of sodium bisulfite and 60 parts of water, stirring for 0.5 hour at 400 r/min, adding 20 parts of methacrylic acid, 20 parts of itaconic acid, 12 parts of ammonium persulfate, 8 parts of sodium bisulfite and 200 parts of water, and stirring for 3 hours to obtain a polycarboxy polymer/hydrotalcite nano composite material;
(2) preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate according to the proportion of 10:40, and dissolving in 600 parts of water to obtain a metal mixed solution;
(3) preparing a polycarboxyl metal complex tanning agent:
and adding the metal mixed solution into 2 parts of polycarboxy polymer/hydrotalcite nano composite material, uniformly stirring, and spray-drying the obtained solution at the inlet temperature of 180 ℃ to obtain the polycarboxy metal complex tanning agent with the self-masking effect.
The properties of leather tanned by the polycarboxyl metal complex tanning agent are as follows:
the test results show that the shrinkage temperature of the finished leather tanned by the polycarboxylic metal complex tanning agent can reach over 90 ℃, and all the performances can reach the industrial standard; due to the permanent electropositivity of the hydrotalcite plate layer, the absorption and combination of anionic dyeing and finishing chemicals such as dye, fatting agent and the like in the later period of leather making are facilitated, so that the finished leather has good dyeing property and softness.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (6)
1. A preparation method of a multi-carboxyl metal complex tanning agent with self-masking effect is characterized by comprising the following steps:
firstly, methacrylic acid and itaconic acid monomers are intercalated into hydrotalcite layers by an ion exchange method, then the monomers are initiated to polymerize in situ to obtain a polycarboxy polymer/hydrotalcite nano composite material, and then the polycarboxy polymer/hydrotalcite nano composite material is mixed with zirconium sulfate and aluminum sulfate to prepare the polycarboxy metal complex tanning agent with the self-masking effect.
2. The preparation method of the multi-carboxyl metal complex tanning agent with the self-masking effect according to claim 1, which is characterized by comprising the following steps of:
step one, preparing a polycarboxy polymer/hydrotalcite nano composite material:
weighing hydrotalcite, adding the hydrotalcite into water, and carrying out ultrasonic treatment for 0.5 h to obtain hydrotalcite dispersion liquid; mixing the hydrotalcite dispersion liquid, methacrylic acid, itaconic acid and water at the temperature of 60-85 ℃, stirring for 2 hours at 700 r/min, adding ammonium persulfate, sodium bisulfite and water, and stirring for 0.5 hour at 400 r/min; then adding methacrylic acid, itaconic acid, ammonium persulfate, sodium bisulfite and water, and stirring for 3 h to obtain a polycarboxy polymer/hydrotalcite nano composite material;
step two, preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate, and dissolving in 200-1000 parts of water to obtain a metal mixed solution;
step three, preparing a polycarboxyl metal complex tanning agent:
and adding the metal mixed solution into a polycarboxy polymer/hydrotalcite nano composite material, uniformly stirring, and spray-drying the obtained solution at the inlet temperature of 180 ℃ to obtain the polycarboxy metal complex tanning agent with the self-masking effect.
3. The preparation method of the polycarboxyl metal complex tanning agent with the self-masking effect as claimed in claim 2, wherein the preparation method comprises the following steps:
in the first step, the amount of hydrotalcite is 1-6% of the total mass of methacrylic acid and itaconic acid, wherein the total mass ratio of methacrylic acid to itaconic acid is 30: 15-90; the total ammonium persulfate dosage is 6-20% of the total mass of the methacrylic acid and the itaconic acid; the total sodium bisulfite dosage is 2-20% of the total mass of methacrylic acid and itaconic acid.
4. The preparation method of the polycarboxyl metal complex tanning agent with the self-masking effect as claimed in claim 2, wherein the preparation method comprises the following steps: in the second step, the mass ratio of the zirconium sulfate to the aluminum sulfate is 3-40: 6-80.
5. The preparation method of the polycarboxyl metal complex tanning agent with the self-masking effect as claimed in claim 2, wherein the preparation method comprises the following steps: in the third step, the mass ratio of the polycarboxy polymer/hydrotalcite nano composite material to the mixture of zirconium sulfate and aluminum sulfate is 0.5-5: 1.
6. A polycarboxy metal complex tanning agent having self-masking properties prepared by the process as claimed in any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111366239.7A CN114164308B (en) | 2021-11-18 | 2021-11-18 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111366239.7A CN114164308B (en) | 2021-11-18 | 2021-11-18 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114164308A true CN114164308A (en) | 2022-03-11 |
| CN114164308B CN114164308B (en) | 2023-12-22 |
Family
ID=80479911
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111366239.7A Active CN114164308B (en) | 2021-11-18 | 2021-11-18 | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114164308B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116397057A (en) * | 2023-05-12 | 2023-07-07 | 陕西科技大学 | Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3423162A (en) * | 1965-03-26 | 1969-01-21 | Bayer Ag | Combined zirconium,aluminum and chrome tannage |
| CN102787182A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Self-alkalization masking zirconium-aluminum-titanium complex tanning agent |
| CN105949369A (en) * | 2016-06-17 | 2016-09-21 | 陕西科技大学 | Preparation method of multi-functional hydrotalcite/polymer nano-composite additive for leather |
| CN110358877A (en) * | 2019-06-04 | 2019-10-22 | 陕西科技大学 | Acrylic/hydrotalcite-like nano tanning agent with layer structure and preparation method thereof and tannage |
-
2021
- 2021-11-18 CN CN202111366239.7A patent/CN114164308B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3423162A (en) * | 1965-03-26 | 1969-01-21 | Bayer Ag | Combined zirconium,aluminum and chrome tannage |
| CN102787182A (en) * | 2012-08-01 | 2012-11-21 | 四川大学 | Self-alkalization masking zirconium-aluminum-titanium complex tanning agent |
| CN105949369A (en) * | 2016-06-17 | 2016-09-21 | 陕西科技大学 | Preparation method of multi-functional hydrotalcite/polymer nano-composite additive for leather |
| CN110358877A (en) * | 2019-06-04 | 2019-10-22 | 陕西科技大学 | Acrylic/hydrotalcite-like nano tanning agent with layer structure and preparation method thereof and tannage |
Non-Patent Citations (1)
| Title |
|---|
| 杨晓燕: "锻烧水滑石纳米材料的调控合成及其鞣制应用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 02, pages 024 - 1150 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116397057A (en) * | 2023-05-12 | 2023-07-07 | 陕西科技大学 | Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers |
| CN116397057B (en) * | 2023-05-12 | 2024-02-02 | 陕西科技大学 | Tanning method for in-situ growth of metal-organic framework nano tanning agent between collagen fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114164308B (en) | 2023-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110358877B (en) | Hydrotalcite-like nano tanning agent with layered structure and preparation method and tanning method thereof | |
| CN101532066B (en) | Preparation method for toughening type leather tanning agent | |
| CN104789715B (en) | One kind is salt-free to exempt from pickling short route less chrome tannage method | |
| CN103276118B (en) | Amphiprotic acrylic resin leather tanning agent | |
| CN114164308A (en) | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof | |
| US10676798B2 (en) | Poly-octavinyl polyhedral oligomeric silsesquioxane-acrylic acid nano composite auxiliary agent for leather and preparation method therefor | |
| CN103255243B (en) | Preparation method of soft acrylic resin leather retanning agent | |
| CN110511388A (en) | A kind of modified hydroxyl acrylic emulsion and preparation method thereof for aqueous coatings for tin plate printing | |
| CN101967257A (en) | Pure acrylic emulsion modified by inorganic nanoparticles and preparation method thereof | |
| Liu et al. | A salt-free pickling and chrome-free tanning technology: a sustainable approach for cleaner leather manufacturing | |
| CN105859954A (en) | Preparing method for waterborne matte acrylic emulsion | |
| CN1224718C (en) | Preparation technology of ving/polymer/modified montmorillonoid nano composite tanoing agent | |
| CN103588935A (en) | Method for preparing modified lignosulfonate water reducing agent with acrylic waste water as raw material | |
| CN103602763B (en) | A kind of have lamellar structure organic-nano silicate composite tanning agent and tannage thereof | |
| CN101240354B (en) | Acrylic resin/SiO2 nano composite tanning agent and preparation method thereof | |
| CN102492079B (en) | Method for preparing nano composite high-absorptivity chrome tanning auxiliary agent by combining polycarboxylic acid copolymer with montmorillonite | |
| CN111321260B (en) | Environment-friendly chromium-free retanning method for leather | |
| CN105949369B (en) | The preparation method of leather multifunctional water talcum/polymer nanocomposite composite assistant | |
| Zhao et al. | Fabrication of effective electromagnetic shielding leather with a chromium-free multi-network structure | |
| CN111057803A (en) | Amphoteric polymer retanning agent for ecological leather manufacturing and preparation method thereof | |
| CN103232566A (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN110862544B (en) | Preparation method of composite adsorption type solid water reducing agent for sulphoaluminate cement | |
| CN108531053B (en) | Preparation method of modified aniline terpolymer/water-based resin composite anticorrosive paint | |
| CN106967969A (en) | A kind of method and modification liquid for obtaining steel body surface vitrification silane composite modified layer | |
| CN110003762A (en) | A kind of preparation method of high tenacity intensity cathode electrodip painting coating |
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 |