CN114164308B - 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
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- CN114164308B CN114164308B CN202111366239.7A CN202111366239A CN114164308B CN 114164308 B CN114164308 B CN 114164308B CN 202111366239 A CN202111366239 A CN 202111366239A CN 114164308 B CN114164308 B CN 114164308B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 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 72
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 72
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 60
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 24
- 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 32
- 239000002114 nanocomposite Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 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
- 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 24
- 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
- 239000006185 dispersion Substances 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
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010985 leather Substances 0.000 abstract description 13
- 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
- 239000000975 dye Substances 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
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000463 material Substances 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
- 230000007547 defect Effects 0.000 description 2
- 230000005611 electricity Effects 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007812 deficiency 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
- 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
- 230000009466 transformation Effects 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 polycarboxylic 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 ℃, ensures that all performances can reach the industry standard, and can promote the absorption and utilization of anionic dyeing and finishing chemicals such as dyes, fatliquoring agents and the like by introducing hydrotalcite with positive charges.
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 to solve the problem of environmental pollution of the traditional chrome tanning method from the source, and also conforms to the market demand of consumers on chrome-free tanning products with high added value and high quality. Currently, chrome-free tanning agents mainly comprise two major 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 comprises zirconium tanning agent, aluminum tanning agent, titanium tanning agent, iron tanning agent and the like. However, the leather prepared by the chrome-free tanning agent has the comprehensive quality which is not comparable with that of chrome-tanned leather. In recent years, the non-chromium metal tanning agent is matched for use, so that the advantages of the non-chromium metal tanning agent are complementary, the defect of the performance of a single non-chromium metal tanning agent is further overcome, and the non-chromium metal tanning agent is widely paid attention to researchers. 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 oversanning, so that the tanning performance of the non-chrome metal tanning agents is reduced. The addition of organic ligands (i.e., masking agents) having hydroxyl, carbonyl, carboxyl and other functional groups to the tanning system can suitably ameliorate the above-described deficiencies of non-chrome metal tanning agents.
Disclosure of Invention
Aiming at the requirements of ecological tanning, the invention provides a multi-carboxyl metal complex tanning agent with a self-masking effect and a preparation method thereof, the use of 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 ℃, the performances of the finished leather can reach the industry standard, and the introduction of hydrotalcite with positive charges can promote the absorption and utilization of anionic dyeing and finishing chemicals such as dyes, fatliquoring agents and the like.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the preparation method of the polycarboxylic metal complex tanning agent with the self-masking effect comprises the steps of firstly, intercalating methacrylic acid and itaconic acid monomers into hydrotalcite layers through an ion exchange method, then, initiating in-situ polymerization of the monomers to obtain a polycarboxylic polymer/hydrotalcite nanocomposite, and then, mixing the polycarboxylic polymer/hydrotalcite nanocomposite with zirconium sulfate and aluminum sulfate to prepare the polycarboxylic metal complex tanning agent with the self-masking effect.
The method specifically comprises the following steps of:
step one, preparing a polycarboxy polymer/hydrotalcite nanocomposite:
weighing hydrotalcite, adding the hydrotalcite into water, and carrying out ultrasonic treatment on the hydrotalcite to obtain hydrotalcite dispersion liquid, wherein the hydrotalcite dispersion liquid is obtained by ultrasonic treatment of 0.5 and h; mixing hydrotalcite dispersion liquid, methacrylic acid, itaconic acid and water at 60-85 ℃, stirring at 700 r/min for 2 h, adding ammonium persulfate, sodium bisulphite and water, and stirring at 400 r/min for 0.5 h; then adding methacrylic acid, itaconic acid, ammonium persulfate, sodium bisulphite and water, and stirring for 3 h to obtain the polycarboxy polymer/hydrotalcite nanocomposite;
step two, preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate, and dissolving the mixed solution in 200-1000 parts of water to obtain a metal mixed solution;
step three, preparing a multi-carboxyl metal complex tanning agent:
and adding the metal mixed solution into the polycarboxy polymer/hydrotalcite nanocomposite, uniformly stirring, and spray-drying the obtained solution, wherein the inlet temperature is 180 ℃, thus obtaining the polycarboxy metal complex tanning agent with self-masking effect.
In the first step, the dosage 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 consumption is 6% -20% of the total mass of methacrylic acid and itaconic acid; the total sodium bisulphite consumption 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 nanocomposite to the mixture of zirconium sulfate and aluminum sulfate is 0.5-5:1.
The polycarboxylic 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 invention prepares the polycarboxy polymer/hydrotalcite nanocomposite by an in-situ polymerization method, and then mixes the polycarboxy polymer/hydrotalcite nanocomposite with zirconium sulfate and aluminum sulfate in a certain proportion to prepare the polycarboxy metal complex tanning agent with self-masking effect. The complex tanning agent can be used for chrome-free tanning of leather, avoids the use of heavy metal chromium, and ensures that the shrinkage temperature of the obtained finished leather can reach more than 90 ℃ and all performances can reach the industry standard; the permanent positive electricity of the hydrotalcite plate layer is beneficial to the absorption and combination of anionic dyeing and finishing chemicals such as dye, fatliquor and the like in the late stage of tanning, so that the finished leather has good dyeing performance and softness.
Detailed Description
The above-described aspects are further described below in conjunction with specific embodiments. It should be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The implementation conditions used in the examples may be further adjusted according to the specific experimental environment, and the implementation conditions not specified are generally those in routine experiments.
The invention prepares the polycarboxy polymer/hydrotalcite nanocomposite material by an in-situ polymerization method, and then mixes the polycarboxy polymer/hydrotalcite nanocomposite material with zirconium sulfate and aluminum sulfate in a certain proportion to obtain the polycarboxy metal complex tanning agent with self-masking effect. The multi-carboxyl polymer containing rich carboxyl is utilized to improve the defect of surface oversanning of the non-chromium metal tanning agent, improve the tanning performance of the non-chromium metal tanning agent, and simultaneously utilize the permanent electropositivity of the hydrotalcite plate layer to promote the absorption and combination of anionic dyeing and finishing chemicals such as dye, fatliquor and the like in the late stage of tanning, so that the finished leather has good dyeing performance and softness.
The preparation method of the polycarboxylic metal complex tanning agent with the self-masking effect specifically comprises the following steps of:
(1) Preparation of polycarboxy polymer/hydrotalcite nanocomposite: weighing 0.45-7.2 parts of hydrotalcite, adding the hydrotalcite into 40 parts of water, and carrying out ultrasonic treatment on the mixture to obtain hydrotalcite dispersion liquid of 0.5-h; 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 at 700 r/min for 2 h, adding 0.9-8 parts of ammonium persulfate, 0.3-8 parts of sodium bisulfite and 33-102 parts of water, and stirring at 400 r/min for 0.5 h; 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-h to obtain a polycarboxy polymer/hydrotalcite nanocomposite;
(2) Preparation of a metal mixed solution: mixing zirconium sulfate and aluminum sulfate according to the proportion of (3-40) to (6-80), and dissolving the mixture in 200-1000 parts of water to obtain a metal mixed solution;
(3) Preparation of a polycarboxylic metal complex tanning agent: and adding the metal mixed solution into a certain amount of polycarboxy polymer/hydrotalcite nanocomposite, uniformly stirring, and spray-drying the obtained solution, wherein the inlet temperature is 180 ℃, thus obtaining the polycarboxy metal complex tanning agent with 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 on the mixture to obtain hydrotalcite dispersion liquid with the ultrasonic treatment of 0.5 h; adding hydrotalcite dispersion, 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 h at 700 r/min, adding 6 parts of ammonium persulfate, 6 parts of sodium bisulphite and 90 parts of water, stirring for 0.5 h at 400 r/min, adding 20 parts of methacrylic acid, 40 parts of itaconic acid, 12 parts of ammonium persulfate, 12 parts of sodium bisulphite and 200 parts of water, and stirring for 3 h to obtain a polycarboxy polymer/hydrotalcite nanocomposite;
(2) Preparation of a metal mixed solution:
zirconium sulfate and aluminum sulfate are mixed according to the proportion of 20:20 and dissolved in 500 parts of water to obtain a metal mixed solution;
(3) Preparation of a polycarboxylic metal complex tanning agent:
adding the metal mixed solution into 3 parts of the polycarboxy polymer/hydrotalcite nanocomposite, uniformly stirring, and spray-drying the obtained solution, wherein the inlet temperature is 180 ℃, thus obtaining the polycarboxy metal complex tanning agent with 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 on the mixture to obtain hydrotalcite dispersion liquid with the ultrasonic treatment of 0.5 h; adding hydrotalcite dispersion, 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 h at 700 r/min, adding 8 parts of ammonium persulfate, 8 parts of sodium bisulphite and 102 parts of water, stirring for 0.5 h at 400 r/min, adding 20 parts of methacrylic acid, 60 parts of itaconic acid, 16 parts of ammonium persulfate, 16 parts of sodium bisulphite and 324 parts of water, and stirring for 3 h to obtain a polycarboxy polymer/hydrotalcite nanocomposite;
(2) Preparation of 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) Preparation of a polycarboxylic metal complex tanning agent:
and adding the metal mixed solution into 1 part of the polycarboxy polymer/hydrotalcite nanocomposite, uniformly stirring, and spray-drying the obtained solution, wherein the inlet temperature is 180 ℃, thus obtaining the polycarboxy metal complex tanning agent with 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 on the mixture to obtain hydrotalcite dispersion liquid with the ultrasonic treatment of 0.5 h; adding hydrotalcite dispersion, 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 h at 700 r/min, adding 4 parts of ammonium persulfate, 4 parts of sodium bisulphite and 80 parts of water, stirring for 0.5 h at 400 r/min, adding 20 parts of methacrylic acid, 20 parts of itaconic acid, 8 parts of ammonium persulfate, 8 parts of sodium bisulphite and 240 parts of water, and stirring for 3 h to obtain a polycarboxy polymer/hydrotalcite nanocomposite;
(2) Preparation of a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate according to a ratio of 40:10, and dissolving the mixed solution in 800 parts of water to obtain a metal mixed solution;
(3) Preparation of a polycarboxylic metal complex tanning agent:
and adding the metal mixed solution into 1.2 parts of the polycarboxy polymer/hydrotalcite nanocomposite, uniformly stirring, and spray-drying the obtained solution, wherein the inlet temperature is 180 ℃, thus obtaining the polycarboxy metal complex tanning agent with the self-masking effect.
Example 4:
(1) Preparation of polycarboxy polymer/hydrotalcite nanocomposite:
3 parts of hydrotalcite is weighed and added into 40 parts of water, and then the hydrotalcite is ultrasonically treated to 0.5 h to obtain hydrotalcite dispersion liquid; adding hydrotalcite dispersion, 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 h at 700 r/min, adding 6 parts of ammonium persulfate, 4 parts of sodium bisulphite and 60 parts of water, stirring for 0.5 h at 400 r/min, adding 20 parts of methacrylic acid, 20 parts of itaconic acid, 12 parts of ammonium persulfate, 8 parts of sodium bisulphite and 200 parts of water, and stirring for 3 h to obtain a polycarboxy polymer/hydrotalcite nanocomposite;
(2) Preparation of a metal mixed solution:
zirconium sulfate and aluminum sulfate are mixed according to the proportion of 10:40 and dissolved in 600 parts of water to obtain a metal mixed solution;
(3) Preparation of a polycarboxylic metal complex tanning agent:
and adding the metal mixed solution into 2 parts of the polycarboxy polymer/hydrotalcite nanocomposite, uniformly stirring, and spray-drying the obtained solution, wherein the inlet temperature is 180 ℃, thus obtaining the polycarboxy metal complex tanning agent with self-masking effect.
The tanning performance of the multi-carboxyl metal complex tanning agent is as follows:
the test results show that the shrinkage temperature of the finished leather can reach more than 90 ℃ and each performance can reach the industry standard when the multi-carboxyl metal is used for tanning with the tanning agent; the permanent positive electricity of the hydrotalcite plate layer is beneficial to the absorption and combination of anionic dyeing and finishing chemicals such as dye, fatliquor and the like in the late stage of tanning, so that the finished leather has good dyeing performance and softness.
The content of the invention is not limited to the examples listed, and any equivalent transformation to the technical solution of the invention that a person skilled in the art can take on by reading the description of the invention is covered by the claims of the invention.
Claims (4)
1. A preparation method of a polycarboxylic metal complex tanning agent with a self-masking effect is characterized by comprising the following steps:
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 polycarboxy polymer/hydrotalcite nanocomposite, and then mixing the polycarboxy polymer/hydrotalcite nanocomposite with zirconium sulfate and aluminum sulfate to prepare a polycarboxy metal complex tanning agent with a self-masking effect;
the method specifically comprises the following steps of:
step one, preparing a polycarboxy polymer/hydrotalcite nanocomposite:
weighing hydrotalcite, adding the hydrotalcite into water, and carrying out ultrasonic treatment on the hydrotalcite to obtain hydrotalcite dispersion liquid, wherein the hydrotalcite dispersion liquid is obtained by ultrasonic treatment of 0.5 and h; mixing hydrotalcite dispersion liquid, methacrylic acid, itaconic acid and water at 60-85 ℃, stirring at 700 r/min for 2 h, adding ammonium persulfate, sodium bisulphite and water, and stirring at 400 r/min for 0.5 h; then adding methacrylic acid, itaconic acid, ammonium persulfate, sodium bisulphite and water, and stirring for 3 h to obtain the polycarboxy polymer/hydrotalcite nanocomposite;
step two, preparing a metal mixed solution:
mixing zirconium sulfate and aluminum sulfate, and dissolving the mixed solution in 200-1000 parts of water to obtain a metal mixed solution;
step three, preparing a multi-carboxyl metal complex tanning agent:
adding the metal mixed solution into the polycarboxy polymer/hydrotalcite nanocomposite, uniformly stirring, and spray-drying the obtained solution, wherein the inlet temperature is 180 ℃, thus obtaining the polycarboxy metal complex tanning agent with self-masking effect;
in the third step, the mass ratio of the polycarboxy polymer/hydrotalcite nanocomposite to the mixture of zirconium sulfate and aluminum sulfate is 0.5-5:1.
2. The method for preparing the polycarboxylic acid metal complex tanning agent with the self-masking effect according to claim 1, which is characterized in that:
in the first step, the dosage 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 consumption is 6% -20% of the total mass of methacrylic acid and itaconic acid; the total sodium bisulphite consumption is 2% -20% of the total mass of methacrylic acid and itaconic acid.
3. The method for preparing the polycarboxylic acid metal complex tanning agent with the self-masking effect according to claim 1, which is characterized in that: in the second step, the mass ratio of the zirconium sulfate to the aluminum sulfate is 3-40:6-80.
4. A polycarboxy metal complex tanning agent with self-masking effect prepared by the preparation method of any one of claims 1-3.
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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 |
-
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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 |
|---|
| 锻烧水滑石纳米材料的调控合成及其鞣制应用研究;杨晓燕;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第第02期期);第B024-1150页 * |
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