CN114807461A - Chrome-free tanning process for carboxyl-containing POSS/polymer composite material and non-chrome metal salt - Google Patents
Chrome-free tanning process for carboxyl-containing POSS/polymer composite material and non-chrome metal salt Download PDFInfo
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 50
- 150000003839 salts Chemical class 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 7
- 239000002184 metal Substances 0.000 title claims abstract description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 156
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 91
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 78
- 235000019253 formic acid Nutrition 0.000 claims abstract description 78
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 60
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 60
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims description 92
- 241000283707 Capra Species 0.000 claims description 47
- 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 17
- MBHFJYDVXSKWNB-UHFFFAOYSA-J aluminum zirconium(4+) disulfate Chemical compound S(=O)(=O)([O-])[O-].[Al+3].S(=O)(=O)([O-])[O-].[Zr+4] MBHFJYDVXSKWNB-UHFFFAOYSA-J 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 4
- 239000010985 leather Substances 0.000 abstract description 33
- 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 abstract description 14
- 230000008719 thickening Effects 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 abstract 3
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 abstract 3
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 abstract 3
- 241000191291 Abies alba Species 0.000 abstract 1
- 102000008186 Collagen Human genes 0.000 description 12
- 108010035532 Collagen Proteins 0.000 description 12
- 229920001436 collagen Polymers 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- 150000003754 zirconium Chemical class 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 description 2
- -1 amino, hydroxyl Chemical group 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000002699 waste material Substances 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
- C14C3/28—Multi-step processes
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- 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 relates to a non-chrome tanning process of carboxyl-containing POSS/polymer composite material and non-chrome metal salt, which comprises the following steps: the method comprises the following steps: pre-tanning: firstly, adding pickled Chinese cabbage and water into a rotary drum, wherein the mass ratio of the pickled Chinese cabbage to the water is 1:1, then adding 8% of table salt based on the mass of the pickled Chinese cabbage, adjusting the pH value of the solution to 6.5 by using a sodium bicarbonate solution, and rotating; adding 6% of POSS/polymer composite material containing carboxyl, and rotating; the pH of the solution was then adjusted to 3.0 using formic acid solution and vortexed. Step two: tanning: adding 8% of non-chromium metal salt, and rotating; then adjusting the pH of the solution to 4.0 by using a sodium bicarbonate solution, and rotating; heating, adding hot water, rotating, standing overnight, rotating the next day, and washing with water. The POSS/polymer composite material containing carboxyl is combined with zirconium sulfate to tanne crust leather, the performance is optimal, the shrinkage temperature is 92.5 ℃, the thickening rate can reach 112.5%, the grain surface is clear, the leather has good fullness, softness and the like, and the problems of over-tanning and uneven permeation of the surface of zirconium tanned leather are solved.
Description
Technical Field
The invention belongs to the field of leather tanning technology, and particularly relates to a non-chrome tanning technology of a carboxyl-containing POSS/polymer composite material and a non-metal salt.
Background
The chrome tanning method occupies the main tanning position in the leather industry with excellent performance, and chrome tanned leather has high wet heat resistance stability, physical and chemical properties and the like, but the absorption rate of the traditional chrome tanning method is 60-70%, the content of chromium in waste liquid is high, the pollution to the environment and the harm to human bodies can be caused, so that the development of an environment-friendly chrome-free tanning agent is one of the research hotspots of people.
Polyhedral oligomeric silsesquioxane (POSS) is an organic/inorganic nano hybrid material with a core-shell structure and has a molecular general formula of (RSiO) 1.5 ） n And n is generally 6, 8, 10, 12 and the like, wherein n =8 is most typical and is named as cage type silsesquioxane. The inorganic part in the POSS is a core of an inorganic cage-shaped structure formed by Si-O-Si bonds, and has good thermal stability, mechanical properties and the like; the organic part is a shell formed by eight organic functional groups R surrounding the organic part, and different active groups such as carboxyl, amino, hydroxyl and the like can be introduced to ensure that the organic part has different functionalities or reactivity. POSS is applied to the leather tanning process, active groups in the POSS act with the skin collagen fibers to endow the skin collagen fibers with certain tanning performance, and the stability, the mechanical property and the like of the skin collagen fibers can be improved.
The non-chromium metal salt tanning agent refers to other metal salt tanning agents except the chromium salt tanning agent, such as aluminum salt, zirconium salt, titanium salt and other tanning agents, and the metal salts are abundant in China, have no pollution and have various advantages in tanning. Among them, aluminum and zirconium salts are the most promising chrome-free tanning agents to replace chromium salts. Aluminum salt tanned leather is white and soft, but aluminum salt and leather collagen fiber are mainly coordinated by single carboxyl, and the aluminum salt tanned leather has the defects of low shrinkage temperature, water washing resistance, thin and flat leather body and the like. The tanning performance of the zirconium salt is only inferior to that of chrome salt and zirconium salt tanning leather, the leather body of the leather is white, and the zirconium salt tanning leather is acid-base resistant, high in shrinkage temperature and stable in property, but has the defects of high water absorption, hard leather body, low softness and the like. The zirconium salt-aluminum salt combined tanning improves the tanning performance of aluminum salt, reduces the cost of zirconium salt, ensures that the grain surface of tanned leather is clear and compact, and the leather body is soft, but has the defects of poor fullness, acid resistance and alkali resistance. Researchers often use aluminum salt or zirconium salt-aluminum salt tanning agents in combination with other tanning agents, and through synergistic effect, leather formation defects are improved and reach use standards.
The preparation process of the carboxyl-containing POSS/polymer composite material is given in the issued patents (in Majia, Jia Lu, Gaosheng, and the like, the octavinyl polyhedral oligomeric silsesquioxane-acrylic acid nano composite auxiliary agent for leather and the preparation method thereof [ P ]. China, ZL201610998893, 2018-01-26.) and the published papers ([ 1] Gaosheng dove, Wangping, Lu, and the like. preparation and application of the polycarboxy P (POSS-MAA) composite material [ J ]. fine chemical engineering, 2018, 35(12):2105-, not described in detail herein, this patent is directed to a process scheme for carboxyl-containing POSS/polymer composites.
Disclosure of Invention
The invention aims to provide a chromium-free tanning process of a carboxyl-containing POSS/polymer composite material and non-chromium metal salt, which improves the humidity-heat resistance stability, filling property, mechanical property, stability and the like of leather, avoids the use of chromium powder and reduces the pollution to the environment.
In order to achieve the above purposes, the invention adopts the technical scheme that:
the chrome-free tanning process of carboxyl POSS/polymer composite material and non-chrome metal salt includes the following steps:
the method comprises the following steps: pre-tanning: firstly, adding goat pickled skin, water with the mass of 100% of that of the goat pickled skin and the temperature of 25-30 ℃ and table salt with the mass of 8% of that of the goat pickled skin into a rotary drum, rotating for 0.5 hour, then firstly adjusting the pH value of the solution to 6.0-7.5 by using a sodium bicarbonate solution with the mass ratio of water to sodium bicarbonate of 20:1, and rotating for 1 hour; adding 2-10% of POSS/polymer composite material containing carboxyl, and rotating for 4-8 h; secondly, regulating the pH of the solution to 5.0-6.0 by using a formic acid solution with the mass ratio of water to formic acid of 10:1, and rotating for 0.5-1 h; then, regulating the pH of the solution to 4.0-5.0 for the third time by using a formic acid solution with the mass ratio of water to formic acid being 10:1, and rotating for 0.5-1 h; fourthly, regulating the pH of the solution to 3.0-4.0 by using a formic acid solution with the mass ratio of water to formic acid of 10:1, and rotating for 0.5-1 h; regulating the pH of the solution to 2.0-3.0 for the fifth time by using a formic acid solution with the mass ratio of water to formic acid of 10:1, and rotating for 0.5-1 h;
step two: tanning: adding 2-10% of non-chromium metal salt, and rotating for 2-5 h; adjusting the pH of the solution to 3.8-4.0 for the sixth time by using a sodium bicarbonate solution with the mass ratio of water to sodium bicarbonate of 20:1, and rotating for 0.5-1 h; and then, a sodium bicarbonate solution with the mass ratio of water to sodium bicarbonate of 20:1 is used for regulating the pH of the solution to 4.0-4.2 for the seventh time, and the solution is rotated for 0.5-1 h; heating to 40 ℃, adding 50 ℃ hot water with the acid bark mass ratio of 1:1, rotating for 2 h, standing overnight, rotating for 1-2 h the next day, and washing with water.
The invention has the following advantages:
1. according to the invention, the POSS/polymer composite material containing carboxyl is firstly introduced into the skin collagen fiber and permeates into the skin collagen fiber, the carboxyl in the POSS/polymer composite material and the amino on the skin collagen fiber form electrovalence bond combination, so that the skin collagen fiber can be endowed with tanning performance, and the POSS has a filling effect on the skin collagen fiber, so that the permeation of non-chromium metal salt is facilitated; introducing non-chromium metal salt (aluminum sulfate, zirconium sulfate), Al 3+ Or Zr 4+ The coordination reaction can be carried out with carboxyl in the POSS/polymer composite material, and can also be carried out with active groups such as amino, carboxyl and the like on the collagen fibers, so that multi-point crosslinking is formed among the collagen fibers, the stability of the collagen fibers is improved, and clean production is realized.
2. The POSS/polymer composite material containing carboxyl is combined with aluminum sulfate to be applied to the tanning process of goat sour skin, compared with aluminum sulfate tanned crust leather, the shrinkage temperature of the combined tanned crust leather can reach 70 ℃, the thickening rate can reach 72%, the combined tanned crust leather is soft and plump, and the shrinkage temperature of the crust leather does not change greatly along with the increase of washing time.
3. According to the invention, the POSS/polymer composite material containing carboxyl is combined with zirconium sulfate and applied to the tanning process of goat pickled leather, compared with crust leather tanned by zirconium sulfate, the shrinkage temperature of the combined tanned crust leather can reach 92 ℃, the thickening rate can reach 104%, the grain surface is clear, the softness is obviously improved, and the problems of over tanning and uneven permeation on the surface of zirconium tanned leather are solved.
4. The POSS/polymer composite material containing carboxyl is combined with zirconium sulfate-aluminum sulfate to be applied to the tanning process of goat sour skin, compared with the crust leather tanned by zirconium sulfate-aluminum sulfate, the shrinkage temperature of the combined tanned crust leather can reach 91 ℃, the thickening rate can reach 93%, the combined tanned crust leather has good fullness, and the acid and alkali resistance of the combined tanned crust leather is obviously improved.
Detailed Description
The present invention is further described in detail by the following examples, which are provided for illustrating the present invention and are not limited to the scope of the present invention, and any technologies implemented based on the above-described contents of the present invention are within the scope of the present invention.
Example 1:
(1) the chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding 30 ℃ water accounting for 100% of the mass of goat pickled skin and 8% of salt accounting for the mass of the goat pickled skin into a rotary drum, then utilizing sodium bicarbonate solution (the mass ratio of the water to the sodium bicarbonate is 20:1, the same below) to regulate the pH value of the solution to be 6.5 for the first time, and rotating for 1 hour; adding 3% of POSS/polymer composite material containing carboxyl, and rotating for 4 h; then, regulating the pH of the solution to 5.5 for the second time by using a formic acid solution (the mass ratio of water to formic acid is 10:1, the same applies below), and rotating for 0.5 h; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 0.5 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 0.5 h; regulating the pH of the solution to 2.5 by using a formic acid solution for the fifth time, and rotating for 0.5 h;
step two: tanning: adding 6% aluminum sulfate, and rotating for 4 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.0 for the seventh time by using a sodium bicarbonate solution, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
(2) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding 30 ℃ water accounting for 100% of the mass of goat pickled skin and 8% of salt accounting for 8% of the mass of the goat pickled skin into a rotary drum, then utilizing a sodium bicarbonate solution to regulate the pH value of the solution to 6.5 for the first time, and rotating for 1 h; adding 3% of POSS/polymer composite material containing carboxyl, and rotating for 4 h; then, regulating the pH value of the solution to 5.5 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 0.5 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 0.5 h; regulating the pH of the solution to 2.5 with formic acid solution for the fifth time, and rotating for 0.5 h;
step two: tanning: adding 6% zirconium sulfate, and rotating for 4 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.0 for the seventh time by using a sodium bicarbonate solution, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
(3) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate-aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding 30 ℃ water accounting for 100% of the mass of goat pickled skin and 6% of salt accounting for 6% of the mass of the goat pickled skin into a rotary drum, then regulating the pH value of the solution to 6.5 by using a sodium bicarbonate solution for the first time, and rotating for 1 h; adding 3% of POSS/polymer composite material containing carboxyl, and rotating for 4 h; then, regulating the pH value of the solution to 5.5 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 0.5 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 0.5 h; regulating the pH of the solution to 2.5 with formic acid solution for the fifth time, and rotating for 0.5 h;
step two: tanning: adding 6% zirconium sulfate-aluminum sulfate (mass ratio is 3.5: 1), and rotating for 4 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.0 for the seventh time by using a sodium bicarbonate solution, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
Example 2:
(1) the chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is regulated to 6.5 for the first time by using a sodium bicarbonate solution, and the rotation is carried out for 1 hour; adding 6% of POSS/polymer composite material containing carboxyl, and rotating for 5 h; then, regulating the pH value of the solution to 5.5 for the second time by using a formic acid solution, and rotating for 1 hour; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 2.5 for the fifth time by using a formic acid solution, and rotating for 1 h;
step two: tanning: adding 8% aluminum sulfate, and rotating for 4 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 hour; regulating the pH of the solution to 4.0 for the seventh time by using a sodium bicarbonate solution, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
(2) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is regulated to 6.5 for the first time by using a sodium bicarbonate solution, and the rotation is carried out for 1 hour; adding 6% of POSS/polymer composite material containing carboxyl, and rotating for 5 h; secondly, regulating the pH value of the solution to 5.5 by using a formic acid solution, and rotating for 1 h; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 2.5 for the fifth time by using a formic acid solution, and rotating for 1 h;
step two: tanning: adding 8% zirconium sulfate, and rotating for 4 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.0 for the seventh time by using a sodium bicarbonate solution, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
(3) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate-aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is regulated to 6.5 for the first time by using a sodium bicarbonate solution, and the rotation is carried out for 1 hour; adding 6% of POSS/polymer composite material containing carboxyl, and rotating for 5 h; then, regulating the pH value of the solution to 5.5 for the second time by using a formic acid solution, and rotating for 1 hour; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 2.5 for the fifth time by using a formic acid solution, and rotating for 1 h;
step two: tanning: adding 8% zirconium sulfate-aluminum sulfate (mass ratio is 4: 1), and rotating for 4 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.0 for the seventh time by using a sodium bicarbonate solution, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
Example 3:
(1) the chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding 30 ℃ water accounting for 100% of the mass of goat pickled skin and 8% of salt accounting for 8% of the mass of the goat pickled skin into a rotary drum, then utilizing sodium bicarbonate solution to regulate the pH value of the solution to 7.0 for the first time, and rotating for 1 h; adding 4.5% of POSS/polymer composite material containing carboxyl, and rotating for 4.5 h; then, regulating the pH value of the solution to 6.0 for the second time by using a formic acid solution, and rotating for 1 hour; then, regulating the pH value of the solution to 5.0 by using a formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 4.0 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 3.0 for the fifth time by using a formic acid solution, and rotating for 1 h;
step two: tanning: adding 7% aluminum sulfate, and rotating for 4.5 h; adjusting the pH of the solution to 4.0 for the sixth time by using a sodium bicarbonate solution, and rotating for 1 hour; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
(2) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding 30 ℃ water accounting for 100% of the mass of goat pickled skin and 6% of salt accounting for 6% of the mass of the goat pickled skin into a rotary drum, then using sodium bicarbonate solution to regulate the pH value of the solution to 7.0 for the first time, and rotating for 1 h; adding 4.5% of POSS/polymer composite material containing carboxyl, and rotating for 4.5 h; then, regulating the pH value of the solution to 6.0 for the second time by using a formic acid solution, and rotating for 1 hour; then, regulating the pH value of the solution to 5.0 by using a formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 4.0 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 3.0 for the fifth time by using a formic acid solution, and rotating for 1 h;
step two: tanning: adding 7% zirconium sulfate, and rotating for 4.5 h; adjusting the pH of the solution to 4.0 for the sixth time by using a sodium bicarbonate solution, and rotating for 1 hour; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
(3) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate-aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding 30 ℃ water accounting for 100% of the mass of the goat pickled skins and the pickled skins and 8% of salt accounting for the mass of the pickled skins into a rotary drum, then regulating the pH value of the solution to 7.0 for the first time by using a sodium bicarbonate solution, and rotating for 1 h; adding 4.5% of POSS/polymer composite material containing carboxyl, and rotating for 4.5 h; then, regulating the pH value of the solution to 6.0 for the second time by using a formic acid solution, and rotating for 1 hour; then, regulating the pH value of the solution to 5.0 by using a formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 4.0 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 3.0 for the fifth time by using a formic acid solution, and rotating for 1 h;
step two: tanning: adding 7% zirconium sulfate-aluminum sulfate (mass ratio is 3: 1), and rotating for 4.5 h; adjusting the pH of the solution to 4.0 for the sixth time by using a sodium bicarbonate solution, and rotating for 1 hour; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 1 hr the next day, and washing with water.
Example 4:
(1) the chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is adjusted to 7.0 for the first time by using a sodium bicarbonate solution, and the solution is rotated for 1 hour; adding 8% of POSS/polymer composite material containing carboxyl, and rotating for 4.5 h; then, regulating the pH value of the solution to 6.0 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 5.0 by using a formic acid solution for the third time, and rotating for 0.5 h; regulating the pH value of the solution to 4.0 for the fourth time by using a formic acid solution, and rotating for 0.5 h; regulating the pH value of the solution to 3.0 for the fifth time by using a formic acid solution, and rotating for 0.5 h;
step two: tanning: adding 9% aluminum sulfate, and rotating for 4.5 h; adjusting the pH of the solution to 4.0 by using a sodium bicarbonate solution for the sixth time, and rotating for 0.5 h; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 2 hr the next day, and washing with water.
(2) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is adjusted to 7.0 for the first time by using a sodium bicarbonate solution, and the solution is rotated for 1 hour; adding 8% of POSS/polymer composite material containing carboxyl, and rotating for 4.5 h; then, regulating the pH value of the solution to 6.0 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 5.0 by using a formic acid solution for the third time, and rotating for 0.5 h; regulating the pH value of the solution to 4.0 for the fourth time by using a formic acid solution, and rotating for 0.5 h; regulating the pH value of the solution to 3.0 for the fifth time by using a formic acid solution, and rotating for 0.5 h;
step two: tanning: adding 9% zirconium sulfate, and rotating for 4.5 h; adjusting the pH of the solution to 4.0 by using a sodium bicarbonate solution for the sixth time, and rotating for 0.5 h; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 2 hr the next day, and washing with water.
(3) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate-aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is adjusted to 7.0 for the first time by using a sodium bicarbonate solution, and the solution is rotated for 1 hour; adding POSS/polymer composite material containing carboxyl, and rotating for 4.5 h; then, regulating the pH value of the solution to 6.0 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 5.0 by using a formic acid solution for the third time, and rotating for 0.5 h; regulating the pH value of the solution to 4.0 for the fourth time by using a formic acid solution, and rotating for 0.5 h; regulating the pH value of the solution to 3.0 for the fifth time by using a formic acid solution, and rotating for 0.5 h;
step two: tanning: adding 9% zirconium sulfate-aluminum sulfate (mass ratio is 5: 1), and rotating for 4.5 h; adjusting the pH of the solution to 4.0 by using a sodium bicarbonate solution for the sixth time, and rotating for 0.5 h; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 2 hr the next day, and washing with water.
Example 5:
(1) the chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 6% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 6% of the mass of the goat pickled skin, adjusting the pH value of the solution to 6.5 for the first time by using a sodium bicarbonate solution, and rotating for 1 h; adding 4% of POSS/polymer composite material containing carboxyl, and rotating for 5 h; then, regulating the pH value of the solution to 5.5 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 2.5 with formic acid solution for the fifth time, and rotating for 0.5 h;
step two: tanning: adding 5% aluminum sulfate, and rotating for 5 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 2 hr the next day, and washing with water.
(2) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is regulated to 6.5 for the first time by using a sodium bicarbonate solution, and the rotation is carried out for 1 hour; adding 4% of POSS/polymer composite material containing carboxyl, and rotating for 5 h; then, regulating the pH value of the solution to 5.5 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 2.5 with formic acid solution for the fifth time, and rotating for 0.5 h;
step two: tanning: adding 5% zirconium sulfate, and rotating for 5 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 2 hr the next day, and washing with water.
(3) The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and zirconium sulfate-aluminum sulfate comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding water at 25 ℃ and salt at 8% of the mass of the goat pickled skin and the pickled skin, wherein the water is 100% of the mass of the goat pickled skin and the water is 100% of the mass of the goat pickled skin, the salt is added into a rotary drum, then, the pH value of the solution is regulated to 6.5 for the first time by using a sodium bicarbonate solution, and the rotation is carried out for 1 hour; adding 4% of POSS/polymer composite material containing carboxyl, and rotating for 5 h; then, regulating the pH value of the solution to 5.5 for the second time by using a formic acid solution, and rotating for 0.5 h; then, regulating the pH value of the solution to 4.5 with formic acid solution for the third time, and rotating for 1 h; regulating the pH value of the solution to 3.5 for the fourth time by using a formic acid solution, and rotating for 1 hour; regulating the pH of the solution to 2.5 with formic acid solution for the fifth time, and rotating for 0.5 h;
step two: tanning: adding 5% zirconium sulfate-aluminum sulfate (mass ratio is 4: 1), and rotating for 5 h; adjusting the pH of the solution to 3.8 by using a sodium bicarbonate solution for the sixth time, and rotating for 1 h; regulating the pH of the solution to 4.2 by using a sodium bicarbonate solution for the seventh time, and rotating for 1 hour; heating to 40 deg.C, adding 50 deg.C hot water, rotating for 2 hr, standing overnight, rotating for 2 hr the next day, and washing with water.
The above embodiments are merely detailed descriptions of the present invention, but the present invention is not limited to the embodiments, and those skilled in the art can make various substitutions and alterations on the technical solution of the present invention by reading the description of the present invention, and all of them are covered by the claims of the present invention and are within the scope of protection.
Claims (4)
1. The chrome-free tanning process of the carboxyl-containing POSS/polymer composite material and non-chrome metal salt is characterized in that: the method comprises the following steps:
the method comprises the following steps: pre-tanning: firstly, adding goat pickled skin, water with the mass of 100% of that of the goat pickled skin and the temperature of 25-30 ℃ and table salt with the mass of 8% of that of the goat pickled skin into a rotary drum, rotating for 0.5 hour, then firstly adjusting the pH value of the solution to 6.0-7.5 by using a sodium bicarbonate solution with the mass ratio of water to sodium bicarbonate of 20:1, and rotating for 1 hour; adding 2-10% of POSS/polymer composite material containing carboxyl, and rotating for 4-8 h; secondly, regulating the pH of the solution to 5.0-6.0 by using a formic acid solution with the mass ratio of water to formic acid of 10:1, and rotating for 0.5-1 h; then, regulating the pH of the solution to 4.0-5.0 for the third time by using a formic acid solution with the mass ratio of water to formic acid being 10:1, and rotating for 0.5-1 h; fourthly, regulating the pH of the solution to 3.0-4.0 by using a formic acid solution with the mass ratio of water to formic acid of 10:1, and rotating for 0.5-1 h; regulating the pH of the solution to 2.0-3.0 for the fifth time by using a formic acid solution with the mass ratio of water to formic acid of 10:1, and rotating for 0.5-1 h;
step two: tanning: adding 2-10% of non-chromium metal salt, and rotating for 2-5 h; adjusting the pH of the solution to 3.8-4.0 for the sixth time by using a sodium bicarbonate solution with the mass ratio of water to sodium bicarbonate of 20:1, and rotating for 0.5-1 h; and then, a sodium bicarbonate solution with the mass ratio of water to sodium bicarbonate of 20:1 is used for regulating the pH of the solution to 4.0-4.2 for the seventh time, and the solution is rotated for 0.5-1 h; heating to 40 ℃, adding 50 ℃ hot water with the acid bark mass ratio of 1:1, rotating for 2 h, standing overnight, rotating for 1-2 h the next day, and washing with water.
2. The non-chrome tanning process of carboxyl-containing POSS/polymer composites with aluminum sulfate as claimed in claim 1, wherein: the non-chromium metal salt is aluminum sulfate or zirconium sulfate-aluminum sulfate with the mass ratio of 2:1-5: 1.
3. The non-chrome tanning process of carboxyl-containing POSS/polymer composites with aluminum sulfate as claimed in claim 1, wherein: 3% -8% of the POSS/polymer composite material containing carboxyl added in the first step.
4. The non-chrome tanning process of carboxyl-containing POSS/polymer composites with aluminum sulfate as claimed in claim 1, wherein: and 5% -9% of non-chromium metal salt added in the second step.
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