CN113372475B - Method for preparing waterproof polymer fatliquor - Google Patents
Method for preparing waterproof polymer fatliquor Download PDFInfo
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- CN113372475B CN113372475B CN202110706985.XA CN202110706985A CN113372475B CN 113372475 B CN113372475 B CN 113372475B CN 202110706985 A CN202110706985 A CN 202110706985A CN 113372475 B CN113372475 B CN 113372475B
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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
- 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
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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Abstract
The invention relates to a method for preparing a waterproof polymer fatliquor, which takes acrylic acid higher alcohol ester as a main reaction raw material, water as a reaction medium and 4,4' -azobis (4-cyano valeric acid) as an initiator to prepare the waterproof polymer fatliquor through miniemulsion polymerization. According to the invention, the acrylic acid higher alcohol ester is used as a monomer, and the hydrophobic long chain of the acrylic acid higher alcohol ester can play a role in lubricating and filling leather fibers, so that the hydrophobicity of the leather is increased; long-chain fatty acid salt, long-chain fatty alcohol maleic acid monoester carboxylate and long-chain fatty alcohol itaconic acid monoester carboxylate are used as emulsifiers, and carboxyl groups of the emulsifiers can form a complex with chromium ions, so that the fatliquor can be fixed; water is used as a medium, so that the environmental protection problem caused by an organic solvent is avoided; the initiator 4,4' -azobis (4-cyanovaleric acid) is used without introducing strongly hydrophilic sulfate groups into the polymer chain. The polymer emulsion obtained by the invention has small particle size and good stability, and the fatted finished leather has better waterproof effect.
Description
Technical Field
The invention relates to the field of leather chemical materials, in particular to the field of waterproof polymer fatliquor.
Background
In recent years, with the improvement of living standard and the enhancement of environmental awareness, consumers have higher requirements on the quality of leather products and pay more attention to the safety, functionality and the like of the leather products. At present, the waterproof performance also becomes one of the most important use values of leather products, so that the preparation of the waterproof fatliquor is concerned widely. Common waterproof materials in the prior tanning production comprise long-chain alkenyl succinic acid, fatty acid metal complex, organosilicon/fluorine waterproof agent, polymer fatliquor and the like. Wherein, the molecule of the polymer fatliquor contains carboxyl with tanning property and long-chain hydrophobic group, which can complete leather fatliquor and waterproof treatment at the same time of tanning, thus being considered as an ideal material for producing waterproof fatliquor.
Solution polymerization is a common method for preparing water-proof polymer fatliquor. For example: strong roche, etc. selects vinyl stearate and acrylic acid monomer to make polymerization, adopts solution polymerization to synthesize WR water-proof polymer fatliquor, and the finished leather treated by WR fatliquor has excellent water-proofing property, 2 hr static water absorption rate is less than 30%, and dynamic bending water-proofing time is greater than 2 hr [ roche is strong, liu hong, yan rain is nourishing ] development of WR water-proof fatliquor [ J ]. Chinese leather, 1999 (17): 13-16 ]. In patent document CN1740344, maleic anhydride or itaconic anhydride and methacrylic acid long-chain alkyl ester are dissolved in xylene, toluene or tetrahydrofuran respectively, and after copolymerization, the mixture reacts with amine, and alkali is added to neutralize the mixture to obtain a waterproof polymer fatliquor; patent document US5316860A uses tert-butyl alcohol as a reaction medium to realize copolymerization of hydrophilic monomers such as acrylic acid, itaconic acid, maleic acid and the like and hydrophobic monomers such as long-chain alkyl acrylate, long-chain alkyl phenyl methacrylate and the like, and the prepared amphiphilic polymer fatliquor provides significant water resistance for leather. In patent document CN103757915A, in ethyl acetate or methyl isobutyl ketone medium, perfluoro-alkenyloxy monomer and alkyl acrylate are subjected to radical copolymerization to prepare a novel environment-friendly waterproof oil. In patent document CN106884063A, isopropyl alcohol, acrylonitrile, vinyl stearate, methacrylic acid, hexadecene, azobisisobutyronitrile, and mercaptan are used to prepare a waterproof fatting agent, and the fatted leather is soft, elastic, and resistant to wet washing. The method for preparing the waterproof polymer fatliquor by using the solution polymerization method is mature, the waterproof performance of the product is excellent, but in a polymerization system, a large amount of organic solvent is used as a reaction medium, so that many problems in the aspects of safety, environmental protection and the like can be caused, and potential harm can be caused to the health of production personnel and users.
At present, the report of preparing the waterproof fatliquor by emulsion polymerization is also available. For example, the Papaver rhoeas et al uses cyclodextrin as a solubilizing carrier and ammonium persulfate as an initiator to realize the ternary polymerization of octadecyl acrylate, dodecyl acrylate and acrylic acid, and leather treated by the ternary copolymer has good waterproofness, softness and thickening rate. Ternary emulsion copolymerization preparation of Comp poppy, cabernet, tanga, wen Qing Liang, zhang Chun Xiao, pengbuyu and acrylic ester amphiphilic polymer and retanning and greasing performance thereof [ J ]. Leather science and engineering, 2020,30 (03): 1-6+34 ]. The Michelson, et al, takes long-chain fatty alcohol-maleic acid monoester and acrylic acid as reaction monomers, takes ammonium persulfate as an initiator, and adopts an active monomer dropwise adding mode to synthesize the maleic acid monoester polymer retanning fatliquor, and the leather thickening rate after the fatliquor treatment is about 30%, and the static water absorption is about 60% (Michelson, lanyunjun, zhoujiafei. Preparation and performance of the maleic acid monoester polymer retanning fatliquor [ J ]. Fine chemical industry, 2009,26 (08): 809-812 ]. However, in the above preparation processes, persulfate is used as an initiator, and sulfate radical with strong hydrophilicity is introduced into a polymer chain segment after the persulfate is decomposed to initiate the polymerization of the monomer. Since the sulfate groups are not easily blocked by chromium salts, the water resistance of the product is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the problems that environmental protection is easily caused by using a large amount of organic solvents as media in the preparation of the existing waterproof polymer fatliquoring agent, and the like, and the waterproof performance of the product is easily reduced by adopting a persulfate initiator, the invention provides a method for preparing the waterproof polymer fatliquoring agent by using water as a reaction medium and 4,4' -azobis (4-cyanovaleric acid) as the initiator through miniemulsion polymerization, and provides a new method for preparing a high-performance green environment-friendly waterproof fatliquoring material.
A method of preparing a water-resistant polymeric fatliquor comprising the steps of:
(1) Mixing, stirring and dissolving the higher alcohol acrylate, the emulsifier and the deionized water, adjusting the pH value to 6-8, and performing ultrasonic dispersion to obtain uniform and stable higher alcohol acrylate pre-emulsion;
(2) Stirring and heating the bottom water to 65-80 ℃, adding one third of initiator, dropwise adding the acrylic acid higher alcohol ester pre-emulsion and the rest initiator after stirring, finishing dropwise adding, heating to 75-85 ℃ after heat preservation for reaction, cooling to below 40 ℃ after reaction, and discharging to obtain the waterproof polymer fatliquor.
According to the present invention, preferably, the higher alcohol acrylate in step (1) is one or more of dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, and octadecyl methacrylate.
According to the present invention, it is preferable that the emulsifier in step (1) is a sodium salt, a potassium salt or an ammonium salt of a long-chain fatty acid such as lauric acid, myristic acid, palmitic acid, stearic acid; carboxylate of long-chain fatty alcohol maleic acid monoester such as lauryl alcohol maleic acid monoester, cetyl alcohol maleic acid monoester and stearyl alcohol maleic acid monoester; one of carboxylate of long-chain fatty alcohol itaconic acid monoester such as lauryl alcohol itaconic acid monoester, cetyl alcohol itaconic acid monoester, stearyl alcohol itaconic acid monoester and isomeric tridecanol itaconic acid monoester;
preferably, the amount of the emulsifier is 10 to 30% by mass of the higher alcohol acrylate.
According to the present invention, preferably, the base selected in the system for adjusting the pH in step (1) is a sodium hydroxide solution, an ammonia water solution or a potassium hydroxide solution.
According to the present invention, it is preferable that the temperature at which the higher alcohol acrylate, the emulsifier and the deionized water are mixed, stirred and dissolved in the step (1) is 20 to 40 ℃.
According to the invention, the ultrasonic dispersion time in the step (1) is preferably 30min to 90min, and the ultrasonic power is preferably 60 to 120W.
According to the present invention, it is preferable that the initiator in the step (2) is 4,4' -azobis (4-cyanovaleric acid) which is used after being neutralized and dissolved with an alkaline solution;
preferably, the total amount of the initiator is 1 to 10% by mass of the higher alcohol acrylate.
According to the invention, preferably, after one third of the initiator is added in the step (2), stirring is carried out for 10min;
preferably, the time for dripping the acrylic acid higher alcohol ester pre-emulsion and the rest initiator is controlled to be 90-150 min;
preferably, the temperature is kept for 30min after the higher alcohol acrylate pre-emulsion and the rest of the initiator are added dropwise.
According to the present invention, it is preferable that the reaction time in the step (2) is 90 to 180min.
According to the invention, the method for preparing a water-repellent polymeric fatliquor, a preferred embodiment, comprises the following steps:
(1) Adding a certain amount of higher alcohol acrylate, an emulsifier and deionized water into a reaction container, stirring and dissolving at 20-40 ℃, adjusting the pH to 6-8, and dispersing for 30-90 min by using ultrasonic with the ultrasonic power of 60-120W to obtain the uniform and stable higher alcohol acrylate pre-emulsion.
(2) Placing a four-mouth bottle provided with a thermometer, a stirring rod, a reflux condenser and a constant-pressure dropping funnel into a constant-temperature water bath, adding a certain amount of bottom water, stirring and heating to 65-80 ℃. Adding one third of initiator, stirring for 10min, and then dropwise adding the acrylic acid higher alcohol ester pre-emulsion and the rest initiator, wherein the dropwise adding time is controlled to be 90-150 min. And (3) after finishing the dropping, keeping the temperature for 30min, heating to 75-85 ℃, reacting for 90-180 min, cooling to below 40 ℃, and discharging to obtain the waterproof polymer fatting agent.
The process route of the invention is as follows:
emulsifying the acrylic acid higher alcohol ester by using an emulsifier, then carrying out ultrasonic dispersion to obtain a uniform and stable pre-emulsion, and carrying out miniemulsion polymerization on the pre-emulsion by using water as a medium to obtain a product.
The invention has the beneficial effects that:
1. according to the invention, the acrylic acid higher alcohol ester is used as a monomer, and the hydrophobic long chain of the acrylic acid higher alcohol ester can play a role in lubricating and filling leather fibers, so that the hydrophobicity of the leather is increased; the long-chain fatty acid salt, the long-chain fatty alcohol maleic acid monoester carboxylate and the long-chain fatty alcohol itaconic acid monoester carboxylate are used as the emulsifier, and the carboxyl of the emulsifier can form a complex with chromium ions, so that the fatliquor can be fixed.
2. The invention adopts water as a reaction medium, and solves the problems of environmental protection, safety and the like caused by the existing solution polymerization method which adopts an organic solvent as a medium.
3. The invention adopts 4,4' -azobis (4-cyanovaleric acid) as an initiator and can not introduce sulfate radicals with strong hydrophilicity into a polymer chain.
4. The invention firstly uses emulsifier to emulsify the acrylic acid higher alcohol ester, then obtains uniform and stable pre-emulsion after ultrasonic dispersion, and carries out miniemulsion polymerization on the pre-emulsion by taking water as medium to obtain the product. The whole preparation process is simple, the operation is easy, and the preparation conditions are mild. The obtained polymer emulsion has small particle size and good stability, and the fatted finished leather has better waterproof effect.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Example 1:
a method of preparing a water-resistant polymeric fatliquor comprising the steps of:
(1) Adding 20g of lauryl acrylate, 3g of lauric acid and a certain amount of deionized water into a beaker, stirring and dissolving, then adjusting the pH value to 6-8, and dispersing for 30min by using ultrasonic with the ultrasonic power of 60W to obtain uniform and stable lauryl acrylate pre-emulsion;
(2) Placing a four-mouth bottle provided with a thermometer, a stirring rod, a reflux condenser and a constant-pressure dropping funnel into a constant-temperature water bath, adding a certain amount of bottom water, stirring and heating to 65 ℃;
preparing an initiator solution: dissolving 0.6g of 4,4' -azobis (4-cyanovaleric acid) in 20g of water, and adjusting the pH to 6-7 with sodium hydroxide solution;
and when the temperature rises to 65 ℃, adding one third of the initiator, stirring for 10min, beginning to dropwise add the lauryl acrylate pre-emulsion and the rest of the initiator, and finishing dropping for 120 min. And (3) after finishing the dropwise adding, keeping the temperature for 30min, heating to 75 ℃, reacting for 90min, cooling to below 40 ℃, and discharging to obtain the waterproof polymer fatting agent.
Example 2:
a method of preparing a water-resistant polymeric fatliquor comprising the steps of:
(1) Adding 10g of octadecyl acrylate, 2.2g of lauric acid and a certain amount of deionized water into a beaker, stirring and dissolving, then adjusting the pH value to 6-8, and dispersing for 50min by using ultrasonic waves with the ultrasonic power of 90W to obtain uniform and stable octadecyl acrylate pre-emulsion;
(2) Placing a four-mouth bottle provided with a thermometer, a stirring rod, a reflux condenser and a constant-pressure dropping funnel into a constant-temperature water bath kettle, adding a certain amount of bottom water, stirring and heating to 70 ℃;
preparing an initiator solution: dissolving 0.5g of 4,4' -azobis (4-cyanovaleric acid) in 20g of water, and adjusting the pH to 6-7 with a sodium hydroxide solution;
and when the temperature rises to 70 ℃, adding one third of the initiator, stirring for 10min, beginning to dropwise add the octadecyl acrylate pre-emulsion and the rest of the initiator, and finishing dropping within 100 min. And (3) after finishing the dropping, keeping the temperature for 30min, heating to 80 ℃, reacting for 90min, cooling to below 40 ℃, and discharging to obtain the waterproof polymer fatting agent.
Example 3:
a method of preparing a water-resistant polymeric fatliquor comprising the steps of:
(1) Adding 20g of lauryl acrylate, stearyl acrylate, 4g of palmitic acid and a certain amount of deionized water into a beaker, stirring and dissolving, then adjusting the pH value to 6-8, and dispersing for 40min by using ultrasonic waves with the ultrasonic power of 80W to obtain uniform and stable acrylic acid higher alcohol ester pre-emulsion;
(2) Placing a four-mouth bottle provided with a thermometer, a stirring rod, a reflux condenser and a constant-pressure dropping funnel into a constant-temperature water bath, adding a certain amount of bottom water, stirring and heating to 75 ℃;
preparing an initiator solution: 1g of 4,4' -azobis (4-cyanovaleric acid) was dissolved in 20g of water and the pH was adjusted to 6-7 with sodium hydroxide solution;
and when the temperature rises to 75 ℃, adding one third of the initiator, stirring for 10min, beginning to dropwise add the acrylic acid higher alcohol ester pre-emulsion and the rest initiator, and finishing dropping within 150min. And (3) after finishing the dropping, keeping the temperature for 30min, heating to 85 ℃, reacting for 90min, cooling to below 40 ℃, and discharging to obtain the waterproof polymer fatting agent.
Example 4:
a method of preparing a water-resistant polymeric fatliquor comprising the steps of:
(1) Adding 20g of lauryl acrylate, 4.4g of lauryl alcohol maleic acid monoester and a certain amount of deionized water into a beaker, stirring and dissolving, then adjusting the pH value to 6-8, and dispersing for 30min by using ultrasonic with the ultrasonic power of 80W to obtain uniform and stable lauryl acrylate pre-emulsion;
(2) Placing a four-mouth bottle provided with a thermometer, a stirring rod, a reflux condenser and a constant-pressure dropping funnel into a constant-temperature water bath, adding a certain amount of bottom water, stirring and heating to 80 ℃;
preparing an initiator solution: dissolving 0.8g of 4,4' -azobis (4-cyanovaleric acid) in 20g of water, and adjusting the pH to 6-7 with a potassium hydroxide solution;
and when the temperature rises to 80 ℃, adding one third of the initiator, stirring for 10min, beginning to dropwise add the lauryl acrylate pre-emulsion and the rest of the initiator, and finishing dropping for 120 min. And (3) after finishing the dropping, keeping the temperature for 30min, heating to 85 ℃, reacting for 90min, cooling to below 40 ℃, and discharging to obtain the waterproof polymer fatting agent.
Example 5:
a method of preparing a water-resistant polymeric fatliquor comprising the steps of:
(1) Adding 20g of octadecyl acrylate, 4g of stearyl itaconic acid monoester and a certain amount of deionized water into a beaker, stirring and dissolving, adjusting the pH value to 6-8, and dispersing for 90min by using ultrasonic with the ultrasonic power of 90W to obtain uniform and stable octadecyl acrylate pre-emulsion;
(2) Placing a four-mouth bottle provided with a thermometer, a stirring rod, a reflux condenser and a constant-pressure dropping funnel into a constant-temperature water bath, adding a certain amount of bottom water, stirring and heating to 70 ℃;
preparing an initiator solution: 1g of 4,4' -azobis (4-cyanovaleric acid) was dissolved in 20g of water and the pH was adjusted to 6-7 with sodium hydroxide solution;
and when the temperature rises to 70 ℃, adding one third of the initiator, stirring for 10min, beginning to dropwise add the octadecyl acrylate pre-emulsion and the rest of the initiator, and finishing dropping within 150min. And (3) after finishing the dropping, keeping the temperature for 30min, heating to 80 ℃, reacting for 90min, cooling to below 40 ℃, and discharging to obtain the waterproof polymer fatting agent.
Experimental example, the waterproof polymer fatliquor prepared by the present invention was subjected to a fatliquor experiment.
The application process I comprises the following steps:
weighing the neutralized first-layer cowhide wet leather, putting the weighed first-layer cowhide wet leather into a rotary drum, adding water with the weight 1.5 times that of the leather and the waterproof polymer fatting agent prepared in the embodiment 5 with the weight 15% of the leather, and rotating for 90min at the temperature of 50 ℃; adding formic acid, adjusting the pH value of the bath liquid to about 3.8, and discharging the liquid; adding water 1.5 times the weight of the skin and chromium powder 2% of the weight of the skin, and rotating at 30 deg.C for 30min; washing out the drum with water, drying the toggling plate, and then softening by a conventional process. The dynamic water-proofing times of the crust leather were determined according to the Bally standard test method. The result shows that the dynamic water-proof times of the crust leather after being treated by the water-proof polymer fatting agent can reach more than 5 ten thousand times.
And the application process II comprises the following steps:
weighing the neutralized two-layer wet cow blue leather, putting the weighed two-layer wet cow blue leather into a rotating drum, adding water with the weight 1.5 times that of the leather and the waterproof polymer fatting agent prepared in the embodiment 2 with the weight 15% of the leather, and rotating the mixture for 90min at the temperature of 50 ℃; adding formic acid, adjusting the pH value of the bath liquid to about 3.8, and discharging the liquid; adding water 1.5 times the weight of the skin and chromium powder 2% of the weight of the skin, and rotating at 30 deg.C for 30min; washing out the drum with water, drying the toggling plate, and then softening by a conventional process. The dynamic waterproofing times of the crust leathers were determined according to the Bally standard test method. The result shows that the dynamic waterproof frequency of the crust leather treated by the waterproof polymer fatliquor reaches more than 3 ten thousand times.
The results show that the finished leather fatliquored by the waterproof polymer fatliquor has a good waterproof effect.
Claims (6)
1. A method of preparing a water-resistant polymeric fatliquor comprising the steps of:
(1) Mixing, stirring and dissolving higher alcohol acrylate, an emulsifier and deionized water, adjusting the pH value to 6-8, and performing ultrasonic dispersion to obtain a uniform and stable higher alcohol acrylate pre-emulsion, wherein the ultrasonic dispersion time is 30min to 90min, and the ultrasonic power is 60-120W;
the acrylic acid higher alcohol ester is one or more of dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate and octadecyl methacrylate;
the emulsifier is sodium salt, potassium salt or ammonium salt of lauric acid, myristic acid, palmitic acid or stearic acid long-chain fatty acid; carboxylate of lauryl, cetyl or stearyl maleic acid monoester long-chain fatty alcohol maleic acid monoester; one of carboxylate of lauryl itaconic acid monoester, cetyl itaconic acid monoester, stearyl itaconic acid monoester or isomeric tridecanol itaconic acid monoester long-chain fatty alcohol itaconic acid monoester; the dosage of the emulsifier is 10 to 30 percent of the mass of the higher alcohol acrylate;
(2) Stirring and heating the bottom water to 65-80 ℃, adding one third of initiator, dropwise adding the acrylic acid higher alcohol ester pre-emulsion and the rest initiator after stirring, finishing dropwise adding, heating to 75-85 ℃ after heat preservation for reaction, cooling to below 40 ℃ after reaction, and discharging to obtain the waterproof polymer fatliquor;
the initiator is 4,4' -azobis (4-cyanovaleric acid) which is used after being neutralized and dissolved by alkaline solution; the total dosage of the initiator is 1 to 10 percent of the mass of the higher alcohol acrylate.
2. The method for preparing a waterproof polymeric fatliquor according to claim 1, wherein the base selected by the system for adjusting the pH in the step (1) is a sodium hydroxide solution, an ammonia water solution or a potassium hydroxide solution.
3. The method for preparing the waterproof polymer fatliquor according to claim 1, wherein the temperature for mixing, stirring and dissolving the higher alcohol acrylate, the emulsifier and the deionized water in the step (1) is 20 to 40 ℃.
4. The method for preparing a waterproof polymeric fatliquor according to claim 1, wherein the step (2) is performed by adding one third of the initiator and then stirring for 10min; dropping the acrylic acid higher alcohol ester pre-emulsion and the rest initiator for 90-150min; and (3) after finishing the dripping of the acrylic acid higher alcohol ester pre-emulsion and the rest initiator, preserving the heat for 30min.
5. The method for preparing the waterproof polymeric fatliquor according to claim 1, wherein the reaction time in the step (2) is 90 to 180min.
6. A method for preparing a water-repellent polymeric fatliquor according to claim 1, characterized in that it comprises the following steps:
(1) Adding a certain amount of higher alcohol acrylate, an emulsifier and deionized water into a reaction container, stirring and dissolving at 20-40 ℃, adjusting the pH to 6-8, and dispersing for 30min-90min by using ultrasonic with the ultrasonic power of 60-120W to obtain a uniform and stable higher alcohol acrylate pre-emulsion;
(2) Placing a four-mouth bottle provided with a thermometer, a stirring rod, a reflux condenser and a constant-pressure dropping funnel into a constant-temperature water bath, adding a certain amount of bottom water, stirring and heating to 65-80 ℃; adding one third of initiator, stirring for 10min, and then beginning to drop the acrylic acid higher alcohol ester pre-emulsion and the rest of initiator, wherein the dropping time is controlled within 90-120min; and (3) after the dripping is finished, keeping the temperature for 30min, heating to 75-85 ℃, reacting for 90-180min, cooling to below 40 ℃, and discharging to obtain the waterproof polymer fatliquor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4236556A1 (en) * | 1992-10-29 | 1994-05-05 | Stockhausen Chem Fab Gmbh | Process for softening / greasing leather and fur |
| DE10010405A1 (en) * | 2000-03-03 | 2001-09-13 | Basf Coatings Ag | Aqueous (meth)acrylate copolymer dispersion, useful for coating agents, is prepared by (co)/graft polymerization in the presence of polymer dispersion using oil soluble free radical initiator |
| DE10250111A1 (en) * | 2002-10-28 | 2004-05-06 | Bayer Ag | Chrome-free, waterproof leather |
| EP2045276A1 (en) * | 2007-10-05 | 2009-04-08 | E.I. Du Pont De Nemours And Company | Fluoropolymer |
| CN101747480B (en) * | 2009-12-30 | 2011-09-14 | 浙江工贸职业技术学院 | Preparation method of polymer fatliquoring agent |
| CN101831024A (en) * | 2010-05-15 | 2010-09-15 | 甘肃宏良皮业股份有限公司 | Method for preparing polymer retanning fat-liquoring agent and retanning fat-liquoring agent |
| CN102153699A (en) * | 2011-03-25 | 2011-08-17 | 温州大学 | Method for preparing leather retanning and greasing agent of poly (long-chain fatty alcohol-itaconic acid monoester) and acrylic acid copolymer |
| CN111154030B (en) * | 2020-02-07 | 2021-04-27 | 四川大学 | Preparation and application of polyoxyalkylene-containing epoxy acrylate polymer active fatliquor |
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2021
- 2021-06-24 CN CN202110706985.XA patent/CN113372475B/en active Active
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