CN109321694A - A kind of preparation method of leather acrylic acid double tanning agent - Google Patents
A kind of preparation method of leather acrylic acid double tanning agent Download PDFInfo
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- CN109321694A CN109321694A CN201811177135.XA CN201811177135A CN109321694A CN 109321694 A CN109321694 A CN 109321694A CN 201811177135 A CN201811177135 A CN 201811177135A CN 109321694 A CN109321694 A CN 109321694A
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- agitator tank
- acrylic acid
- water
- metering
- temperature
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of preparation methods of leather acrylic acid double tanning agent, acrylic acid and water are put in proportion into the first metering agitator tank, initiator and water are put in proportion into the second metering agitator tank, neutralizer is put in proportion into third metering agitator tank, regulator isopropanol and solution of sodium bisulfite are put in proportion into the 4th metering agitator tank, a certain amount of water is added to reaction kettle, certain temperature is warming up to start that the first metering agitator tank is added dropwise simultaneously to reaction kettle, second metering agitator tank and the 4th metering agitator tank solution, it is warming up to certain temperature after being added dropwise and is stirred to react a period of time, it is cooled to certain temperature again, start that third metering agitator tank neutralizer is added dropwise, it is neutralized to PH=6.3~6.5, it is warming up to certain temperature and is stirred to react a period of time, water is added to be adjusted so as to acrylic acid double tanning agent, product effective content 30 ± 2 %, PH=6.3~6.8；Environment-protecting clean of the present invention, product can effectively improve leather uniformity, fillibility, grain planarization, reduce position it is poor.
Description
Technical field
The invention belongs to leather agent production technical fields, and in particular to a kind of preparation side of leather acrylic acid double tanning agent
Method.
Background technique
It experienced a series of manufacturing procedure from raw material skin to leather finish, wherein retanning procedures are the key that process hides processing
One of process.Leather composite tanning agent is one of most commonly used leather chemicals in process hides process, it not only affects leather
Richness, flexibility and sense organ, and great shadow is generated to physical mechanical properties such as the tensile strength of leather, extensibility
It rings, or even can also assign the special service performance such as finished leather Water-proof and oil-proof, anti-pollution, fire-retardant, preventing atomization by retanning.
Retanning is one of important essential process in leather making process, is known as " Golden Touch " of process hides, passes through
Fullness, the degree of packing, diminution position difference of leather etc. can be improved in retanning, is also beneficial to the operation of subsequent arranging process.Acrylic acid
Quasi polymer retanning agent has preferable water dispersible and with the good binding ability of leather, and filling effect is strong, thickens work to leather
With obvious, the good flexibility of leather, fullness and elasticity can also impart to.Meanwhile carboxyl and chromium in acrylic acid double tanning agent
Complexing power it is strong, thus the absorption of chromium can be promoted and fixed effect is played to chromium, leather containing with free chromium can be substantially reduced
Amount reduces the chrome content in waste water.In addition, acrylic acid double tanning agent is fast light ageing-resistant good, the color of energy aufhellung chrome leather is especially suitable
Production for white light color leather.
With the development of leather industry, leather composite tanning agent is also had higher requirement, it, can by proper choice of retanning agent
To change the perception and inherent quality of leather, its commodity value is significantly improved, therefore the developing state of Duo Zu Fen ﹑ performance retanning agent exists
Field of leather has tremendous development.
Summary of the invention
The purpose of the invention is to overcome the deficiencies in the prior art, and provide a kind of environmental protection, cleaning, good product quality
The preparation method of leather acrylic acid double tanning agent.
The object of the present invention is achieved like this: a kind of preparation method of leather acrylic acid double tanning agent includes the following steps:
Acrylic acid and water are put into according to a certain percentage in the first metering agitator tank, initiator and water are put into the second meter by a certain percentage
It measures in agitator tank, neutralizer is put by a certain percentage in third metering agitator tank, by regulator isopropanol and regulator sulfurous
Sour hydrogen sodium solution is put by a certain percentage in the 4th metering agitator tank, and a certain amount of water is added into reaction kettle, is warming up to certain
At a temperature of into reaction kettle start simultaneously be added dropwise first metering agitator tank, second metering agitator tank and the 4th measure agitator tank in
Three kinds of solution after being added dropwise, are continuously heating to after being stirred to react a period of time under certain temperature, then be cooled to certain temperature
Under, start the neutralizer being added dropwise in third metering agitator tank, is neutralized to PH=6.3~6.5, and be warming up under certain temperature and stir
After reacting a period of time, water is added to adjust to obtain product acrylic acid double tanning agent, products obtained therefrom effective content be 30 ± 2%, PH=6.3~
6.8。
Preferably, water is first added into reaction kettle, opens heating, temperature control is put at 74~76 DEG C, then into reaction kettle
Mass ratio is the initiator of acrylic monomers quality 0.3% in the first metering agitator tank, stirs 10~15 minutes subsequent temperature of continuing rising,
Temperature is controlled at 88~92 DEG C, starts while being added dropwise the first metering agitator tank, the second metering agitator tank and the 4th metering agitator tank
In three kinds of solution, time for adding was controlled at 120~150 minutes, and after being added dropwise, temperature is controlled at 90~92 DEG C, and stirring is anti-
It answers 1~1.5 hour, is then turned on cooling water temperature, temperature is controlled at 60~65 DEG C, starts to be added dropwise in third metering agitator tank
Neutralizer, after being added dropwise, temperature is controlled at 65~68 DEG C, is stirred to react 1~1.5 hour, water is added to adjust to obtain product propylene
Sour retanning agent, products obtained therefrom effective content are 30 ± 2%, PH=6.3~6.8.
Preferably, the Bing Xi Suan ﹑ initiator, regulator isopropanol, the sulfurous acid in regulator solution of sodium bisulfite
Hydrogen sodium, neutralizer mass ratio be 50~70:0.09~0.11:0.18~0.21:0.17~0.2:25~30.
Preferably, the initiator is potassium peroxydisulfate or ammonium persulfate.
Preferably, the neutralizer is the sodium hydroxide solution of concentration 30%.
Preferably, the water is deionized water.
By adopting the above-described technical solution, the beneficial effects of the present invention are: preparation method provided by the present invention not only
Environmental protection realizes clean manufacturing without the generation of waste water and exhaust gas, has also produced the product of high quality, products obtained therefrom propylene
Sour retanning agent can effectively improve the uniformity, fillibility, grain planarization of leather, can effectively reduce leather potential difference.
Specific embodiment
Below by embodiment, technical solution of the present invention is described in further detail.
Embodiment 1
By in acrylic acid 600kg and deionized water 70kg investment the first metering agitator tank, stir evenly, the mistake for being 0.8% by concentration
In potassium sulfate solution 125kg investment the second metering agitator tank, the sodium hydroxide solution 900kg that concentration is 30% is put into third meter
It measures in agitator tank, in the 4th metering agitator tank of solution of sodium bisulfite 105kg investment for being 4.5% by isopropanol 14kg and concentration,
It stirs evenly；
Deionized water 1000kg is added into enamel reaction still, opens heating, temperature is controlled at 76 DEG C, put into reaction kettle
Potassium sulfate 1.8kg, stirring continue to heat up after ten minutes, and temperature is controlled at 88 DEG C, start first is added dropwise simultaneously and measure agitator tank, the
Three kinds of solution in two metering agitator tanks, the 4th metering agitator tank, time for adding are controlled 150 minutes, after being added dropwise, temperature
Control is stirred to react 1.5 hours at 90 DEG C, is then turned on cooling water temperature, and temperature is maintained at 60 DEG C, starts that third metering is added dropwise
Sodium hydroxide solution in agitator tank, after being added dropwise, temperature is controlled at 65 DEG C, is stirred to react 1.5 hours, is added deionized water tune
It is whole to effective content 29.8%, detect PH=6.7.
Embodiment 2
By in acrylic acid 500kg and deionized water 70kg investment the first metering agitator tank, stir evenly, the over cure for being 1% by concentration
In sour the second metering of potassium solution 125kg investment agitator tank, the sodium hydroxide solution 900kg that concentration is 30% is put into third metering
In agitator tank, in the 4th metering agitator tank of solution of sodium bisulfite 100kg investment for being 4.5% by isopropanol 12kg and concentration, stir
It mixes uniformly；
Deionized water 1000kg is added into enamel reaction still, opens heating, temperature is controlled at 75 DEG C, put into reaction kettle
Potassium sulfate 1.5kg stirs 12 minutes subsequent temperature of continuing rising, and temperature is controlled at 91 DEG C, starts first is added dropwise simultaneously and measures agitator tank, the
Three kinds of solution in two metering agitator tanks and the 4th metering agitator tank, time for adding was controlled at 130 minutes, after being added dropwise, temperature
Degree control is stirred to react 1.2 hours at 91 DEG C, is then turned on cold cooling water temperature, and temperature is maintained at 63 DEG C, starts that third is added dropwise
The sodium hydroxide solution in agitator tank is measured, after being added dropwise, temperature is controlled at 67 DEG C, is stirred to react 1.2 hours, is added deionization
Water is adjusted to effective content 30.5%, detects PH=6.5.
Embodiment 3
By in acrylic acid 700kg and deionized water 90kg investment the first metering agitator tank, stir evenly, the mistake for being 0.8% by concentration
In potassium sulfate solution 140kg investment the second metering agitator tank, the sodium hydroxide solution 1100kg that concentration is 30% is put into third meter
It measures in agitator tank, in the 4th metering agitator tank of solution of sodium bisulfite 125kg investment for being 4.5% by isopropanol 18kg and concentration,
It stirs evenly；
Deionized water 1000kg is added into enamel reaction still, opens heating, temperature is controlled at 74 DEG C, put into reaction kettle
Potassium sulfate 2.1kg, stirring continue to heat up after ten minutes, and temperature is controlled at 92 DEG C, start first is added dropwise simultaneously and measure agitator tank, the
Three kinds of solution in two metering agitator tanks and the 4th metering agitator tank, time for adding was controlled at 120 minutes, after being added dropwise, temperature
Degree control is stirred to react 1 hour at 92 DEG C, is then turned on cooling water temperature, and temperature is maintained at 65 DEG C, starts that third metering is added dropwise
Sodium hydroxide solution in agitator tank, after being added dropwise, temperature is controlled at 68 DEG C, is stirred to react 1 hour, deionized water is added to adjust
To effective content 30.2%, PH=6.4 are detected.
In above-described embodiment, acrylic acid, initiator, regulator isopropanol, regulator are sub- in product effective content, that is, product
The content of sodium hydrogensulfite and neutralizer in sodium bisulfate, the professional standard of the effective content are 30 ± 2%.
Wherein, product effective content can detect to obtain by baking oven oven drying method, and experimental article is temperature-regulating oven and vierics
Ware, the specific steps are as follows:
(1) glassware is dry；
(2) temperature-regulating oven is preheated to 40 DEG C, and glassware weighs a certain amount of acrylic acid double tanning agent, is put into baking oven；Heating 4
Hour, moisture content is dried and is removed, remaining substance after drying is weighed, the ratio of acrylic acid double tanning agent before calculating remaining substance and drying
Value, obtains acrylic acid double tanning agent product effective content.
Here is the testing result of acrylic acid double tanning agent stability of emulsion obtained by above-mentioned 3 embodiments:
The wherein measurement of 1:9 diluting emulsion stability: taking hot distilled water 90m1 to have in plug graduated cylinder in 100m1,10m1 sample be added,
Stopper bottle stopper, stir l min(up and down about 30 times) be sufficiently mixed shake up after stood for 24 hours in 25~35 DEG C of incubators, observe it
Supernatant liquid delamination investigates its emulsion intercalation method.
The wherein measurement of 1:2 diluting emulsion stability: it takes hot distilled water 80m1 to have in plug graduated cylinder in 100m1,20m1 is added
Sample, stoppers bottle stopper, stirs l min(up and down about 30 times) shake up after stood for 24 hours in 25~35 DEG C of incubators, observe its supernatant liquid
Delamination investigates its emulsion intercalation method.
Here is that the one provided by the invention using effect to acrylic acid double tanning agent obtained by above-mentioned 3 embodiments is tested
Example, the specific steps are as follows:
(1) it neutralizes: being put into 3 pieces of sheepskin chrome leather 1, No. 2, No. 3 in 3 rotary drums, be separately added into the 35 of skin sample quality 200%
DEG C water, add the sodium bicarbonate of skin sample quality 0.8%, turn 20min, the PH of bath foam in rotary drum is made to reach 5.5~6.0；
(2) it washes: 35 DEG C of water of skin sample quality 300% is added, wash 10min, skin sample quality is separately added into 3 rotary drums
150% 35 DEG C of water and 1,2, the 3 gained acrylic acid double tanning agent of embodiment of skin sample quality 10%, after turning 90min, then are separately added into
The formic acid of skin sample quality 0.5%, turns 15min, then is separately added into the formic acid of skin sample quality 0.5%, turns 30min, looks into bath foam in rotary drum
For PH=3.5~3.6, washes out and rouse, it is dry；
(3) it detects: 3 pieces of sheepskin chrome leather samples 1 obtained by step (2), No. 2, No. 3 progress thickness and tensile strength is detected, it is real
Test the result is as follows:
It can be seen that present invention gained acrylic acid double tanning agent good emulsion stability, preparation method provided by the present invention not only ring
It protects, without the generation of waste water and exhaust gas, realizes clean manufacturing, also produced the product of high quality, products obtained therefrom acrylic acid
Retanning agent can effectively improve the uniformity, fillibility, grain planarization of leather, can effectively reduce leather potential difference.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations, although
Referring to above-described embodiment, invention is explained in detail, it should be understood by a person of ordinary skill in the art that still may be used
With modifications or equivalent substitutions are made to specific embodiments of the invention, and repaired without departing from any of spirit and scope of the invention
Change or equivalent replacement, is intended to be within the scope of the claims of the invention.
Claims (6)
1. a kind of preparation method of leather acrylic acid double tanning agent, which comprises the steps of: by acrylic acid and water according to
In certain proportion investment the first metering agitator tank, initiator and water are put into according to a certain percentage in the second metering agitator tank, it will
Neutralizer is put into according to a certain percentage in third metering agitator tank, and regulator isopropanol and regulator solution of sodium bisulfite are pressed
According in the 4th metering agitator tank of certain proportion investment；A certain amount of water is added into reaction kettle, is warming up under certain temperature to anti-
The three kinds of solution for starting in kettle while being added dropwise in the first metering agitator tank, the second metering agitator tank and the 4th metering agitator tank are answered,
After being added dropwise, it is continuously heating to after being stirred to react a period of time under certain temperature, then be cooled under certain temperature, starts to be added dropwise
Third measures the neutralizer in agitator tank, is neutralized to PH=6.3~6.5, and is warming up under certain temperature and is stirred to react a period of time
Afterwards, water is added to adjust to obtain product acrylic acid double tanning agent, products obtained therefrom effective content is 30 ± 2%, PH=6.3~6.8.
2. the preparation method of leather acrylic acid double tanning agent according to claim 1, it is characterised in that: first add into reaction kettle
Water opens heating, and temperature is controlled at 74~76 DEG C, then putting into mass ratio into reaction kettle is acrylic acid in the first metering agitator tank
The initiator of monomer mass 0.3%, stirs 10~15 minutes subsequent temperature of continuing rising, and temperature controls at 88~92 DEG C, starts while being added dropwise
Three kinds of solution in first metering agitator tank, the second metering agitator tank and the 4th metering agitator tank, time for adding control 120~
150 minutes, after being added dropwise, temperature was controlled at 90~92 DEG C, is stirred to react 1~1.5 hour, is then turned on cooling water temperature,
Temperature controls the neutralizer for starting to be added dropwise at 60~65 DEG C in third metering agitator tank, after being added dropwise, temperature control 65~
It 68 DEG C, being stirred to react 1~1.5 hour, water is added to adjust to obtain product acrylic acid double tanning agent, products obtained therefrom effective content is 30 ±
2%, PH=6.3~6.8.
3. the preparation method of leather acrylic acid double tanning agent according to claim 1 or 2, it is characterised in that: the Bing Xi Suan ﹑
Initiator, regulator isopropanol, the sodium hydrogensulfite in regulator solution of sodium bisulfite, neutralizer mass ratio be 50~
70:0.09~0.11:0.18~0.21:0.17~0.2:25~30.
4. the preparation method of leather acrylic acid double tanning agent according to claim 1 or 2, it is characterised in that: the initiator
For potassium peroxydisulfate or ammonium persulfate.
5. the preparation method of leather acrylic acid double tanning agent according to claim 1 or 2, it is characterised in that: the neutralizer
For the sodium hydroxide solution of concentration 30%.
6. the preparation method of leather acrylic acid double tanning agent according to claim 1 or 2, it is characterised in that: the water is to go
Ionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811177135.XA CN109321694A (en) | 2018-10-10 | 2018-10-10 | A kind of preparation method of leather acrylic acid double tanning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811177135.XA CN109321694A (en) | 2018-10-10 | 2018-10-10 | A kind of preparation method of leather acrylic acid double tanning agent |
Publications (1)
| Publication Number | Publication Date |
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| CN109321694A true CN109321694A (en) | 2019-02-12 |
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ID=65261875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811177135.XA Withdrawn CN109321694A (en) | 2018-10-10 | 2018-10-10 | A kind of preparation method of leather acrylic acid double tanning agent |
Country Status (1)
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| CN (1) | CN109321694A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058787A (en) * | 1990-08-08 | 1992-02-19 | 丹东市皮革化工厂 | Making method of multi-functional acrylic acid double tanning agent |
| CN101851310A (en) * | 2010-06-09 | 2010-10-06 | 齐河力厚化工有限公司 | Preparation method of acrylic acid retanning agents |
| CN102212624A (en) * | 2010-04-06 | 2011-10-12 | 孙昕 | Novel leather tanning agent and preparation method thereof |
-
2018
- 2018-10-10 CN CN201811177135.XA patent/CN109321694A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058787A (en) * | 1990-08-08 | 1992-02-19 | 丹东市皮革化工厂 | Making method of multi-functional acrylic acid double tanning agent |
| CN102212624A (en) * | 2010-04-06 | 2011-10-12 | 孙昕 | Novel leather tanning agent and preparation method thereof |
| CN101851310A (en) * | 2010-06-09 | 2010-10-06 | 齐河力厚化工有限公司 | Preparation method of acrylic acid retanning agents |
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Application publication date: 20190212 |
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