CN109354644A - A kind of preparation method of the acrylic acid double tanning agent for leather - Google Patents
A kind of preparation method of the acrylic acid double tanning agent for leather Download PDFInfo
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- CN109354644A CN109354644A CN201811177122.2A CN201811177122A CN109354644A CN 109354644 A CN109354644 A CN 109354644A CN 201811177122 A CN201811177122 A CN 201811177122A CN 109354644 A CN109354644 A CN 109354644A
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- agitator tank
- acrylic acid
- leather
- metering
- water
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- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F2/00—Processes of polymerisation
-
- 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
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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 acrylic acid double tanning agent for leather, acrylic acid, acrylamide and water are put in proportion into premix kettle and are pumped into the first metering agitator tank after mixing evenly, regulator solution of sodium bisulfite is put in proportion into the second metering agitator tank, neutralizer is put in proportion into third metering agitator tank, initiator and water are put in proportion into the 4th metering agitator tank；Reaction kettle adds water, maleic anhydride is proportionally added under certain temperature, the 4th metering agitator tank initiator solution is added after hydrolysis stirring, then start that the first metering agitator tank and the second metering agitator tank solution are added dropwise simultaneously, it is stirred to react a period of time after being added dropwise, is down to certain temperature and starts that third metering agitator tank neutralizer is added dropwise, obtain acrylic acid double tanning agent after adding water to adjust, product effective content is 30 ± 2%, PH=5.5~6.5；Environment-protecting clean of the present invention, products obtained therefrom have many advantages, such as to make that leather permeability is good, makes leathering consolidation, leather is made to have voluptuousness, keep leather acidproof.
Description
Technical field
The invention belongs to leather agent production technical fields, and in particular to a kind of system of the acrylic acid double tanning agent for leather
Preparation 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 acrylic acid double tanning agent for leather.
The object of the present invention is achieved like this: a kind of preparation method of the acrylic acid double tanning agent for leather, including such as
Acrylic acid, acrylamide and water: being put into premix kettle by lower step according to a certain percentage, is pumped into the first metering stirring after mixing evenly
In tank, regulator solution of sodium bisulfite is put into according to a certain percentage in the second metering agitator tank, by neutralizer according to certain
Ratio is put into third metering agitator tank, and initiator and water are put into according to a certain percentage in the 4th metering agitator tank；To reaction
A certain amount of water is added in kettle, opens heating, is heated under certain temperature, maleic anhydride is added according to a certain percentage, hydrolysis is stirred
After mixing a period of time, the initiator solution being added at one time in the 4th metering agitator tank at a certain temperature stirs after addition
Reaction a period of time is mixed, then starts to be added dropwise simultaneously in the first metering agitator tank and the second metering agitator tank at a certain temperature
Two kinds of solution after being added dropwise, are stirred to react a period of time, then be cooled under certain temperature, start that third metering stirring is added dropwise
Neutralizer in tank after being added dropwise, is stirred to react a period of time at a certain temperature, and it is multiple to obtain product acrylic acid after adding water to adjust
Tanning agent, products obtained therefrom effective content are 30 ± 2%, PH=5.5~6.5.
Preferably, a certain amount of water is added into reaction kettle, opens heating, temperature is controlled at 60~65 DEG C, to reaction kettle
Middle that a certain amount of maleic anhydride is added, then hydrolysis stirring 30~35 minutes is warming up to 82~84 DEG C, disposable into reaction kettle
The initiator solution in the 4th metering agitator tank is added, after addition, is stirred to react 10~15 minutes, then starts to drip simultaneously
The first metering agitator tank person second is added to measure two kinds of solution in agitator tank, dropping temperature control is at 84~86 DEG C, time for adding
Control was at 60~90 minutes, and after being added dropwise, temperature is controlled at 84~87 DEG C, is stirred to react 2.5~3 hours, is then turned on cold
But water cools down, and temperature controls the neutralizer for starting to be added dropwise at 55~60 DEG C in third metering agitator tank, after being added dropwise, temperature
Control is stirred to react 1~1.5 hour at 55~60 DEG C, obtains product acrylic acid double tanning agent after adding water to adjust, products obtained therefrom effectively contains
Amount is 30 ± 2%, PH=5.5~6.5.
Preferably, the mixture of the acrylic acid and acrylamide, the bisulfite in regulator solution of sodium bisulfite
Sodium, initiator, maleic anhydride, neutralizer mass ratio be 90~110:15~20:15~18:20~25:20~30, wherein third
The mass ratio of olefin(e) acid, acrylamide are as follows: 65~90:7.5~12.5.
Preferably, the neutralizer is the ammonium hydroxide or monoethanolamine of concentration 28%.
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, has also produced the product of high quality without the generation of waste water and exhaust gas, and it is multiple to improve leather
The effect of tan, leather permeability is good, makes leathering consolidation, leather is made to have meat with making for prepared product acrylic acid double tanning agent
The advantages that feeling, keeping leather acidproof.
Specific embodiment
Below by embodiment, technical solution of the present invention is described in further detail.
Embodiment 1
It is stand-by by stirring evenly in acrylic acid 160kg, acrylamide 20kg and water 120kg investment the first metering agitator tank, it will be dense
Degree measures in agitator tank for use for 7.8% solution of sodium bisulfite 45kg investment second, and the ammonium hydroxide 70kg that concentration is 28% is thrown
Enter in third metering agitator tank, in the 4th metering agitator tank of ammonium persulfate solution 50kg investment for being 16% by concentration；
Water 250kg is added into enamel reaction still, opens heating, temperature is controlled at 60 DEG C, and horse is added at one time into reaction kettle
Carry out acid anhydrides 65kg, hydrolysis stirring 30 minutes is warming up to 82 DEG C, measures the ammonium persulfate solution in agitator tank for the 4th and disposably adds
Enter in reaction kettle, after addition, be stirred to react 10 minutes, then starts that the first metering agitator tank and the second metering are added dropwise simultaneously
Two kinds of solution in agitator tank, at 84 DEG C, time for adding is controlled 90 minutes for dropping temperature control, after being added dropwise, temperature control
It at 84 DEG C, is stirred to react 3 hours, is then turned on cooling water temperature, temperature is maintained at 55 DEG C, starts that third metering agitator tank is added dropwise
In ammonium hydroxide, after being added dropwise, temperature control at 55 DEG C, be stirred to react 1.5 hours, add water 50kg adjust after obtain product propylene
Sour retanning agent, through testing product effective content 30.1%, PH=5.6.
Embodiment 2
It is stand-by by stirring evenly in acrylic acid 130kg, acrylamide 15kg and water 90kg investment the first metering agitator tank, it will be dense
Degree measures in agitator tank for use for 7.8% solution of sodium bisulfite 30kg investment second, and the ammonium hydroxide 55kg that concentration is 28% is thrown
Enter in third metering agitator tank for use, it is stand-by in the 4th metering agitator tank of ammonium persulfate solution 40kg investment for being 16% by concentration；
Water 200kg is added into enamel reaction still, opens heating, temperature is controlled at 63 DEG C, and horse is added at one time into reaction kettle
Carry out acid anhydrides 55Kg, hydrolysis stirring 30 minutes is warming up to 83 DEG C, measures the ammonium persulfate solution in agitator tank for the 4th and disposably adds
Enter in reaction kettle, after addition, be stirred to react 10 minutes, then starts that the first metering agitator tank and the second metering are added dropwise simultaneously
Two kinds of solution in agitator tank, at 85 DEG C, time for adding was controlled at 75 minutes for dropping temperature control, after being added dropwise, temperature control
System is at 85 DEG C.Insulation reaction 2.7 hours, it is then turned on cooling water temperature, temperature is maintained at 58 DEG C, starts dropwise addition third metering and stirs
The ammonium hydroxide in tank is mixed, after being added dropwise, temperature is controlled at 58 DEG C, is stirred to react 1.3 hours, obtains product after adding water 50kg to adjust
Acrylic acid double tanning agent, through testing product effective content 29.5%, PH=5.8.
Embodiment 3
It is stand-by by stirring evenly in acrylic acid 180kg, acrylamide 25kg and water 140kg investment the first metering agitator tank, it will be dense
Degree measures in agitator tank for use for 7.8% solution of sodium bisulfite 55kg investment second, and the ammonium hydroxide 90kg that concentration is 28% is thrown
Enter in third metering agitator tank for use, it is stand-by in the 4th metering agitator tank of ammonium persulfate solution 62kg investment for being 16% by concentration；
Water 250kg is added into enamel reaction still, opens heating, temperature is controlled at 65 DEG C, and horse is added at one time into reaction kettle
Carry out acid anhydrides 73kg, hydrolysis stirring 30 minutes is warming up to 84 DEG C, measures the ammonium persulfate solution in agitator tank for the 4th and disposably adds
Enter in reaction kettle, after addition, be stirred to react 10 minutes, then starts that the first metering agitator tank and the second metering are added dropwise simultaneously
Two kinds of solution in agitator tank, at 86 DEG C, time for adding was controlled at 60 minutes for dropping temperature control, after being added dropwise, temperature control
System is stirred to react 2.5 hours at 87 DEG C, is then turned on cooling water temperature, and temperature is controlled at 60 DEG C, is started dropwise addition third metering and is stirred
The ammonium hydroxide in tank is mixed, after being added dropwise, temperature is controlled at 60 DEG C, is stirred to react 1 hour, obtains product third after adding water 50kg to adjust
Olefin(e) acid retanning agent, through testing product effective content 30.2%, PH=6.2.
In above-described embodiment, acrylic acid, acrylamide, regulator solution of sodium bisulfite in product effective content, that is, product
In sodium hydrogensulfite, initiator ammonium persulfate, maleic anhydride and neutralizer content, the professional standard of the effective content is 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 leather acrylic acid double tanning agent, is put into baking oven；
Heating 4 hours is dried moisture content and is removed, and remaining substance after drying is weighed, acrylic acid retanning before calculating remaining substance and drying
The ratio of agent 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
Oil slick delamination investigates the stability of its solution.
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 oil slick
Delamination investigates the stability of its solution.
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:
| Sheepskin chrome leather sample | No. 1 | No. 2 | No. 3 |
| Thickness (mm) | 0.78 | 0.81 | 0.83 |
| Permeability | It is good | It is good | It is good |
| Compactibility | By force | By force | By force |
| Tensile strength (N/m ㎡) | 10.1 | 10.2 | 10.5 |
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, improved leather retanning
Effect, prepared product acrylic acid double tanning agent has and makes that leather permeability is good, makes leathering consolidation, leather is made to have meat
The advantages that feeling, keeping leather acidproof.
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 (5)
1. a kind of preparation method of the acrylic acid double tanning agent for leather, which comprises the steps of: by acrylic acid,
Acrylamide and water put into premix kettle according to a certain percentage, are pumped into the first metering agitator tank after mixing evenly, by regulator Asia
Sodium bisulfate is put into according to a certain percentage in the second metering agitator tank, and neutralizer is put into third metering according to a certain percentage
In agitator tank, initiator and water are put into according to a certain percentage in the 4th metering agitator tank；It is added into reaction kettle a certain amount of
Water is opened heating, is heated under certain temperature, maleic anhydride is added according to a certain percentage, after hydrolysis stirring a period of time, one
Determine the initiator solution being added at one time in the 4th metering agitator tank at temperature, a period of time is stirred to react after addition, so
Start two kinds of solution being added dropwise in the first metering agitator tank and the second metering agitator tank simultaneously at a certain temperature afterwards, is added dropwise
Afterwards, it is stirred to react a period of time, then is cooled under certain temperature, starts the neutralizer being added dropwise in third metering agitator tank, is added dropwise
After, it is stirred to react a period of time at a certain temperature, obtains product acrylic acid double tanning agent after adding water to adjust, products obtained therefrom is effective
Content is 30 ± 2%, PH=5.5~6.5.
2. the preparation method of the acrylic acid double tanning agent according to claim 1 for leather, it is characterised in that: to reaction kettle
It is middle that a certain amount of water is added, heating is opened, temperature is controlled at 60~65 DEG C, a certain amount of maleic anhydride is added into reaction kettle,
Hydrolysis stirring 30~35 minutes, is then warming up to 82~84 DEG C, is added at one time in the 4th metering agitator tank into reaction kettle
Initiator solution after addition, is stirred to react 10~15 minutes, then starts that the first metering agitator tank person second is added dropwise simultaneously
Two kinds of solution in agitator tank are measured, at 84~86 DEG C, time for adding was controlled at 60~90 minutes for dropping temperature control, was dripped
Bi Hou, temperature are controlled at 84~87 DEG C, are stirred to react 2.5~3 hours, are then turned on cooling water temperature, temperature control 55~
60 DEG C, start the neutralizer being added dropwise in third metering agitator tank, after being added dropwise, temperature is controlled at 55~60 DEG C, is stirred to react 1
~1.5 hours, product acrylic acid double tanning agent is obtained after adding water to adjust, products obtained therefrom effective content is 30 ± 2%, PH=5.5~6.5.
3. the preparation method of the acrylic acid double tanning agent according to claim 1 or 2 for leather, it is characterised in that: described
The mixture of acrylic acid and acrylamide, the sodium hydrogensulfite in regulator solution of sodium bisulfite, initiator, maleic anhydride,
The mass ratio of neutralizer is 90~110:15~20:15~18:20~25:20~30, wherein the quality of acrylic acid, acrylamide
Than are as follows: 65~90:7.5~12.5.
4. the preparation method of the acrylic acid double tanning agent according to claim 1 or 2 for leather, it is characterised in that: described
Neutralizer is the ammonium hydroxide or monoethanolamine of concentration 28%.
5. the preparation method of the acrylic acid double tanning agent according to claim 1 or 2 for leather, it is characterised in that: described
Water is deionized water.
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| CN201811177122.2A CN109354644A (en) | 2018-10-10 | 2018-10-10 | A kind of preparation method of the acrylic acid double tanning agent for leather |
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| CN201811177122.2A CN109354644A (en) | 2018-10-10 | 2018-10-10 | A kind of preparation method of the acrylic acid double tanning agent for leather |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349891A (en) * | 2021-12-02 | 2022-04-15 | 许昌鑫瑞德化工科技有限公司 | Preparation method of low-temperature synthetic acrylic acid retanning agent for leather |
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| US4737549A (en) * | 1985-08-16 | 1988-04-12 | Bayer Aktiengesellschaft | Terpolymers of maleic acid anhydride, (meth)acrylic acid, and (meth)acrylonitrile |
| US5425784A (en) * | 1992-01-21 | 1995-06-20 | Basf Aktiengesellschaft | Polymeric tanning agents |
| CN101323886A (en) * | 2008-07-04 | 2008-12-17 | 陕西科技大学 | Preparation of acrylic polymer retanning agent for highly elastic leather retanning |
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2018
- 2018-10-10 CN CN201811177122.2A patent/CN109354644A/en active Pending
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| US4737549A (en) * | 1985-08-16 | 1988-04-12 | Bayer Aktiengesellschaft | Terpolymers of maleic acid anhydride, (meth)acrylic acid, and (meth)acrylonitrile |
| US5425784A (en) * | 1992-01-21 | 1995-06-20 | Basf Aktiengesellschaft | Polymeric tanning agents |
| CN101323886A (en) * | 2008-07-04 | 2008-12-17 | 陕西科技大学 | Preparation of acrylic polymer retanning agent for highly elastic leather retanning |
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| --: "柔软性聚合物鞣剂", 《中国皮革》 * |
| 彭波等: "丙烯酸类聚合物鞣剂合成与应用", 《皮革科学与工程》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349891A (en) * | 2021-12-02 | 2022-04-15 | 许昌鑫瑞德化工科技有限公司 | Preparation method of low-temperature synthetic acrylic acid retanning agent for leather |
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Application publication date: 20190219 |