CN115584368B - Surfactant for leather fatliquoring and preparation method thereof - Google Patents
Surfactant for leather fatliquoring and preparation method thereof Download PDFInfo
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- CN115584368B CN115584368B CN202211262699.XA CN202211262699A CN115584368B CN 115584368 B CN115584368 B CN 115584368B CN 202211262699 A CN202211262699 A CN 202211262699A CN 115584368 B CN115584368 B CN 115584368B
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/326—Polymers modified by chemical after-treatment with inorganic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to a surfactant for leather greasing and a preparation method thereof, belonging to the technical field of emulsifiers. The surfactant comprises the following components in parts by weight: 40-60 parts of modified active agent, 18-25 parts of oil-in-water active agent, 4-8 parts of microcrystalline wax, 5-8 parts of neutral oil and 2-5 parts of glycerol; the molecular structure of the surfactant is a crab-shaped structure, the polyether segment and the sulfonic group in the middle have good hydrophilicity, the four groups of branched short alkane chains at the end parts have good compatibility with animal oil and vegetable oil, in the using process, the oil-in-water type surfactant forms small-particle-size emulsion droplets which are compatible with the hydrophilic end of the modified surfactant, and the branched short alkane chains at the end parts are compatibly coated under the action of tension to form an oil-in-water-in-oil structure of oil-in-oil.
Description
Technical Field
The invention belongs to the technical field of emulsifiers, and particularly relates to a surfactant for leather fatliquoring and a preparation method thereof.
Background
Leather is one of the main fiber materials used by people, a series of complex processing procedures are needed for obtaining high-quality leather, and a greasing procedure is one of the important procedures for obtaining high-quality leather. Grease or a lubricating material is introduced into the leather as a leather fatting agent and can permeate among the collagen fibers, an oil film is formed on the surface of the collagen fibers, the collagen fibers are lubricated, the strength of the leather fibers is effectively improved, and the crosslinking of the fibers is promoted, so that the softness and fullness of the leather are effectively improved, and the physical and mechanical properties of the leather can be improved.
Surfactants are generally used as emulsifying components of the fatliquor, which requires that the used surfactants have good emulsifying property and dispersibility, so that grease forms stable emulsion and is easy to permeate into leather, and the fatliquor emulsion can be uniformly distributed in the leather and absorbed by leather fibers.
The common amphoteric surface active is taken as the emulsification treatment of fatting agent among the prior art, and it has anion and cationic hydrophilic group simultaneously, has good emulsification to the grease, compares with traditional anionic surfactant and has certain improvement, but does not promote the leather performance apparently, and the quantity that increases surfactant also is not obvious effect, consequently, this application aims at developing novel surfactant, promotes the infiltration effect of fatting agent to the leather.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention aims to provide a surfactant for leather fatliquoring and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a surfactant for leather fatliquoring comprises the following components in parts by weight:
40-60 parts of modified active agent, 18-25 parts of oil-in-water active agent, 4-8 parts of microcrystalline wax, 5-8 parts of neutral oil and 2-5 parts of glycerol.
The modified active agent is prepared by the following method:
step A1: mixing di-n-butylamine, acetone and triethylamine, heating to 50-55 ℃, setting the stirring speed at 180-300rpm, adding epoxy chloropropane, performing reflux reaction for 30-40min, then adding a potassium tert-butoxide solution, performing reduced pressure rotary evaporation, removing a solvent and excessive epoxy chloropropane, washing a rotary evaporation product with ice water, performing centrifugal liquid separation, taking organic phase, and drying to obtain an epoxy intermediate;
further, the using ratio of di-n-butylamine, epoxy chloropropane, acetone, triethylamine and potassium tert-butoxide is 1mol:1.2-1.4mol:100-120mL:1.6-2mL:0.1-0.2g.
The specific reaction process is as follows:
step A2: mixing the epoxy intermediate, polyether glycol, toluene and triphenylphosphine, setting the stirring speed to be 80-100rpm, heating to 100-110 ℃, carrying out reflux reaction for 60-80min, and carrying out reduced pressure rotary evaporation to remove toluene after the reaction is finished to obtain a bridging substrate;
furthermore, the molar ratio of epoxy group to hydroxyl group of the epoxy intermediate and the polyether diol is 1.1-1.2, the dosage of toluene is 1.2 times of the total volume of the epoxy intermediate and the polyether diol, and the dosage of triphenylphosphine is 0.07-0.11wt%.
Further, the polyether glycol has an average molecular weight of 600 to 1000.
The specific reaction process is as follows:
step A3: mixing dioxane and deionized water as a solvent, adding sulfamic acid and urea, stirring for dissolving, mixing with a bridging substrate, heating to 85-95 ℃, setting the stirring speed at 800-900rpm, stirring at a high speed for reaction for 1.5-2h, dropwise adding a sodium hydroxide solution after the reaction until the pH value of a reaction system is 6.0, and carrying out reduced pressure rotary evaporation to remove the solvent to obtain a modified active agent;
further, the dosage ratio of the bridging matrix, sulfamic acid, urea, dioxane and deionized water is 100g:8.5-10g:1-1.2g:60-100mL:120-180mL.
The specific reaction process is as follows:
further, the oil-in-water active agent is selected from Tween 80 and an emulsifier BRIJ-721.
Further, the neutral oil is selected from one of 32# -68# white oil.
A preparation method of a surfactant for leather fatliquoring specifically comprises the following steps: mixing microcrystalline wax, neutral oil and glycerol, heating, stirring for dissolving, adding the modified active agent and the oil-in-water type active agent, shearing at a high speed of 1200rpm for 10-20min, and performing vacuum defoaming treatment to obtain the surfactant for leather fatliquoring.
The invention has the beneficial effects that:
the surfactant for greasing leather prepared by the invention is prepared by compounding a self-made oleophilic type modified active agent and a commercially available oil-in-water type active agent, has good emulsification effect on leather grease, so that the grease can fully permeate into leather fibers to infiltrate the leather fibers, and the softness and elasticity of the leather are improved;
the modified active agent takes di-n-butylamine and epoxy chloropropane as raw materials to perform catalytic reaction in an alkaline environment to prepare a ring-branched oxygen intermediate containing epoxy groups and short alkane chains, polyether diol reacts with the epoxy groups of the epoxy intermediate to bridge the epoxy intermediate, the prepared bridging substrate contains four groups of bridging substrates of the short alkane chains, finally, sulfamic acid is used for modifying hydroxyl groups on the bridging substrate molecules, hydrophilic sulfonic acid groups are grafted, the prepared modified active agent is in a crab-shaped structure, the middle polyether segment and the sulfonic acid groups have good hydrophilicity, the four groups of the branched short alkane chains at the end parts have good compatibility with animal oil and vegetable oil, and in the using process, the oil-in-water type active agent forms small-particle-size emulsion droplets which are compatible with the hydrophilic end of the modified active agent, and the end-branched short alkane chains are compatible and coated under the tension effect to form an oil-in-oil structure.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In this example, the specific implementation process of preparing the surfactant for leather greasing is as follows:
1) Preparation of modified active Agents
a1, adding di-n-butylamine, acetone and triethylamine into a reaction kettle, mixing for 10min at 120rpm, heating to 50 ℃, setting the stirring speed to 180rpm, adding epoxy chloropropane, performing reflux reaction for 40min, dissolving potassium tert-butoxide in tert-butyl alcohol, adding a potassium tert-butoxide solution into the reaction kettle, performing reduced pressure rotary evaporation, mainly removing an acetone solvent and excessive epoxy chloropropane, taking out a rotary evaporation product, washing the rotary evaporation product with ice water, placing washing liquid in a centrifuge for centrifugal liquid separation, and taking an organic phase, filtering and drying by using a neutral drying tube to obtain an epoxy intermediate;
in the above reaction, the use ratio of di-n-butylamine, epichlorohydrin, acetone, triethylamine and potassium tert-butoxide is 1mol:1.2mol:100mL of: 1.6mL:0.1g, determined as 0.2mol of di-n-butylamine during the course of the experiment.
a2, adding the epoxy intermediate, polyether glycol, toluene and triphenylphosphine into a reaction kettle, mixing for 15min at 300rpm, heating to 100 ℃, performing reflux reaction for 80min, and performing reduced pressure rotary evaporation to remove the toluene solvent after the reaction is finished to obtain a bridging substrate;
in the above reaction, the polyether diol is selected from polyethylene glycol ether, having an average molecular weight of 600, provided by jie pioneer chemical limited, guangzhou, and the polyether diols in the following examples are provided by the same company, wherein the molar ratio of epoxy group to hydroxyl group of the epoxy intermediate and the polyether diol is 1.1, the amount of toluene is 1.2 times the total volume of the epoxy intermediate and the polyether diol, the amount of triphenylphosphine is 0.07wt% of the total amount of the three, and 35g of the epoxy intermediate is used for quantification in the implementation process.
a3, adding dioxane and deionized water into a reaction kettle, stirring and mixing to serve as a solvent, adding sulfamic acid and urea, stirring and dissolving, adding a bridging substrate, mixing, heating to 85 ℃, setting the stirring speed to be 800rpm, stirring at a high speed for reaction for 2 hours, dropwise adding a sodium hydroxide solution after the reaction until the pH value of a reaction system is 6.0, and carrying out reduced pressure rotary evaporation to remove dioxane and deionized water to obtain a modified active agent;
in the above reaction, the amount ratio of the bridging substrate, sulfamic acid, urea, dioxane and deionized water is 100g:8.5g:1g:60mL of: 180mL, quantified as 100g of bridging matrix.
2) Preparation of the surfactant
s1, taking the materials according to the following weight ratio:
40 parts of modified active agent, which is prepared in the embodiment;
oil-in-water active agents selected from tween 80, supplied by southeast tomahu chemical limited, the following examples used the same batch of raw materials, 25 parts;
microcrystalline wax, selected from # 80 microcrystalline wax, available from Henan Yuyan wax industries, inc. the following examples used the same batch of starting material, 4 parts;
neutral oil, selected from 32# white oil, supplied by Suzhou Sesens oil products, inc., 8 parts of the same company feedstock was used in the following examples;
glycerin, provided by Weichang Chenxing chemical technology Co., ltd, chemical pure grade reagent, the following example used the same batch of raw materials, 2 parts;
in this example, 2g was used as 1 part to satisfy the sample preparation.
And s2, adding the microcrystalline wax, the neutral oil and the glycerol into a high-speed shearing machine, heating to 50 ℃, stirring until the microcrystalline wax, the neutral oil and the glycerol are completely dissolved, adding the modified active agent and the oil-in-water type active agent, setting the stirring speed to be 1200rpm, carrying out high-speed shearing for 10min, vacuumizing to-0.1 MPa, and carrying out defoaming treatment for 20min to obtain the surfactant for leather fatliquoring.
Example 2
The surfactant for leather fatliquoring is prepared in the embodiment by the following specific implementation process:
1) Preparation of modified active Agents
a1, adding di-n-butylamine, acetone and triethylamine into a reaction kettle, mixing for 10min at 120rpm, heating to 55 ℃, setting the stirring speed to 300rpm, adding epoxy chloropropane, performing reflux reaction for 30min, dissolving potassium tert-butoxide in tert-butyl alcohol, adding a potassium tert-butoxide solution into the reaction kettle, performing reduced pressure rotary evaporation, mainly removing an acetone solvent and excessive epoxy chloropropane, taking out a rotary evaporation product, washing with ice water, placing washing liquid into a centrifuge for centrifugal liquid separation, and filtering and drying an organic phase by using a neutral drying tube to obtain an epoxy intermediate;
in the above reaction, the use ratio of di-n-butylamine, epichlorohydrin, acetone, triethylamine and potassium tert-butoxide is 1mol:1.4mol:120mL of: 2mL of: 0.2g, determined as 0.2mol of di-n-butylamine during the course of the experiment.
a2, adding the epoxy intermediate, polyether diol, toluene and triphenylphosphine into a reaction kettle, mixing for 15min at 300rpm, heating to 110 ℃, performing reflux reaction for 60min, and performing reduced pressure rotary evaporation to remove the solvent toluene after the reaction is finished to obtain a bridging substrate;
in the above reaction, the polyether diol is selected from polyethylene glycol ether, the molar ratio of epoxy group and hydroxyl group of the epoxy intermediate and polyether diol is 1.1, the amount of toluene is 1.2 times of the total volume of the epoxy intermediate and polyether diol, and the amount of triphenylphosphine is 0.09wt% of the total amount of the three, and 35g of epoxy intermediate is used for quantification in the implementation process, wherein the average molecular weight is 800.
a3, adding dioxane and deionized water into a reaction kettle, stirring and mixing to serve as a solvent, adding sulfamic acid and urea, stirring and dissolving, adding a bridging matrix, mixing, heating to 95 ℃, setting the stirring speed to be 900rpm, stirring at a high speed for reaction for 1.5 hours, dropwise adding a sodium hydroxide solution after reaction until the pH value of a reaction system is 6.0, and carrying out reduced pressure rotary evaporation to remove dioxane and deionized water to obtain a modified active agent;
in the above reaction, the dosage ratio of the bridging matrix, sulfamic acid, urea, dioxane and deionized water is 100g:9.2g:1.1g:80mL of: 160mL, quantified as 100g of bridging matrix.
2) Preparation of the surfactant
s1, taking materials according to the following weight ratio:
the modifying active agent is prepared by the embodiment and 60 parts;
an oil-in-water active agent selected from the group consisting of emulsifier BRIJ-721, available from Beijing lingbao Tech & ltd., in the following examples, 18 parts of the same batch of raw materials was used;
8 parts of microcrystalline wax;
neutral oil selected from No. 46 white oil, 6 parts;
5 parts of glycerol;
in this example, 1 part is 1.5g for satisfying the sample preparation detection.
And s2, adding the microcrystalline wax, the neutral oil and the glycerol into a high-speed shearing machine, heating to 50 ℃, stirring until the microcrystalline wax, the neutral oil and the glycerol are completely dissolved, adding the modified active agent and the oil-in-water type active agent, setting the stirring speed to be 1200rpm, carrying out high-speed shearing for 15min, vacuumizing to-0.1 MPa, and carrying out defoaming treatment for 20min to obtain the surfactant for leather fatliquoring.
Example 3
The surfactant for leather fatliquoring is prepared in the embodiment by the following specific implementation process:
1) Preparation of modified active Agents
a1, adding di-n-butylamine, acetone and triethylamine into a reaction kettle, mixing for 10min at 120rpm, heating to 55 ℃, setting the stirring speed to 240rpm, adding epoxy chloropropane, performing reflux reaction for 35min, dissolving potassium tert-butoxide in tert-butyl alcohol, adding a potassium tert-butoxide solution into the reaction kettle, performing reduced pressure rotary evaporation, mainly removing an acetone solvent and excessive epoxy chloropropane, taking out a rotary evaporation product, washing with ice water, placing washing liquid into a centrifuge for centrifugal liquid separation, and filtering and drying an organic phase by using a neutral drying tube to obtain an epoxy intermediate;
in the above reaction, the use ratio of di-n-butylamine, epichlorohydrin, acetone, triethylamine and potassium tert-butoxide is 1mol:1.3mol:110mL:1.8mL:0.15g, in the course of practice, was determined as 0.2mol of di-n-butylamine.
a2, adding the epoxy intermediate, polyether diol, toluene and triphenylphosphine into a reaction kettle, mixing at 300rpm for 20min, heating to 110 ℃, performing reflux reaction for 80min, and performing reduced pressure rotary evaporation to remove the solvent toluene after the reaction is finished to obtain a bridging substrate;
in the above reaction, the polyether diol is selected from polyethylene glycol ether, having an average molecular weight of 1000, provided by jie pioneer chemical limited, guangzhou, and the polyether diols in the following examples are provided by the same company, wherein the molar ratio of epoxy group to hydroxyl group of the epoxy intermediate and the polyether diol is 1.1, the amount of toluene is 1.5 times the total volume of the epoxy intermediate and the polyether diol, the amount of triphenylphosphine is 0.07wt% of the total amount of the three, and 35g of the epoxy intermediate is used for quantification in the implementation process.
a3, adding dioxane and deionized water into a reaction kettle, stirring and mixing to serve as a solvent, adding sulfamic acid and urea, stirring and dissolving, adding a bridging matrix, mixing, heating to 90 ℃, setting the stirring speed to be 900rpm, stirring at a high speed for reaction for 1.8 hours, dropwise adding a sodium hydroxide solution after reaction until the pH value of a reaction system is 6.0, and carrying out reduced pressure rotary evaporation to remove dioxane and deionized water to obtain a modified active agent;
in the above reaction, the amount ratio of the bridging substrate, sulfamic acid, urea, dioxane and deionized water is 100g:10g:1.2g:100mL of: 120mL, quantified as 100g of bridging matrix.
2) Preparation of the surfactant
s1, taking materials according to the following weight ratio:
modifying activator, self-made in this example, 50 parts;
oil-in-water active agents selected from tween 80, supplied by southeast tomahu chemical limited, the following examples used the same batch of raw materials, 20 parts;
microcrystalline wax, selected from # 80 microcrystalline wax, provided by Henan Yuyang wax industries, inc., the following examples used the same batch of raw materials, 5 parts;
neutral oil, selected from # 68 white oil, supplied by Suzhou Sesens oil Co., ltd, the following examples used the same batch of raw material, 8 parts;
glycerin, provided by Weichang Chenxing chemical technology Co., ltd, chemical pure grade reagent, the following examples used the same batch of raw materials, 4 parts;
in this example, 1 part is 1.8g for satisfying the sample preparation detection.
And s2, adding the microcrystalline wax, the neutral oil and the glycerol into a high-speed shearing machine, heating to 50 ℃, stirring until the microcrystalline wax, the neutral oil and the glycerol are completely dissolved, adding the modified active agent and the oil-in-water type active agent, setting the stirring speed to be 1200rpm, carrying out high-speed shearing for 20min, vacuumizing to-0.1 MPa, and carrying out defoaming treatment for 20min to obtain the surfactant for leather fatliquoring.
Example 4
In this example, the specific implementation process of preparing the surfactant for leather greasing is as follows:
1) Preparation of modified active Agents
a1, adding di-n-butylamine, acetone and triethylamine into a reaction kettle, mixing for 10min at 120rpm, heating to 55 ℃, setting the stirring speed to 300rpm, adding epoxy chloropropane, performing reflux reaction for 35min, dissolving potassium tert-butoxide in tert-butyl alcohol, adding a potassium tert-butoxide solution into the reaction kettle, performing reduced pressure rotary evaporation, mainly removing an acetone solvent and excessive epoxy chloropropane, taking out a rotary evaporation product, washing with ice water, placing washing liquid into a centrifuge for centrifugal liquid separation, and taking an organic phase, filtering and drying by using a neutral drying tube to obtain an epoxy intermediate;
in the above reaction, the use ratio of di-n-butylamine, epichlorohydrin, acetone, triethylamine and potassium tert-butoxide is 1mol:1.3mol:120mL of: 1.8mL:0.2g, determined as 0.2mol of di-n-butylamine during the course of the experiment.
a2, adding the epoxy intermediate, polyether glycol, toluene and triphenylphosphine into a reaction kettle, mixing for 15min at 300rpm, heating to 105 ℃, performing reflux reaction for 70min, and performing reduced pressure rotary evaporation to remove the solvent toluene after the reaction is finished to obtain a bridging substrate;
in the above reaction, the polyether glycol is selected from polyethylene glycol ether, has an average molecular weight of 800, and is provided by jie innovative chemical company ltd, guangzhou, and the polyether glycol in the following examples is provided by the company, wherein the molar ratio of epoxy group to hydroxyl group of the epoxy intermediate and the polyether glycol is 1.2, the amount of toluene is 1.2 times of the total volume of the epoxy intermediate and the polyether glycol, the amount of triphenylphosphine is 0.08wt% of the total amount of the three, and 35g of the epoxy intermediate is used for quantification in the implementation process.
a3, adding dioxane and deionized water into a reaction kettle, stirring and mixing to serve as a solvent, adding sulfamic acid and urea, stirring and dissolving, adding a bridging substrate, mixing, heating to 90 ℃, setting the stirring speed to be 900rpm, stirring at a high speed for reaction for 2 hours, dropwise adding a sodium hydroxide solution after the reaction until the pH value of a reaction system is 6.0, and carrying out reduced pressure rotary evaporation to remove dioxane and deionized water to obtain a modified active agent;
in the above reaction, the amount ratio of the bridging substrate, sulfamic acid, urea, dioxane and deionized water is 100g:9.5g:1.1g:90mL of: 140mL, quantified as 100g of bridging matrix.
2) Preparation of the surfactant
s1, taking materials according to the following weight ratio:
a modifying active agent, prepared in the example, 48 parts;
oil-in-water active agents selected from tween 80, provided by southeast yen rapid chemical limited, the following examples used the same batch of raw materials, 22 parts;
microcrystalline wax, selected from # 80 microcrystalline wax, supplied by Henan Yuyang wax industries, inc., the following examples used the same batch of raw materials, 7 parts;
neutral oil, selected from 46# white oil, supplied by Suzhou Sesens oil Co., ltd, the following examples used the same batch of raw material, 7 parts;
glycerin, provided by Weichang Chenxing chemical technology Co., ltd, chemical pure grade reagent, the following examples used the same batch of raw materials, 4 parts;
in this example, 2g was used as 1 part to satisfy the sample preparation.
And s2, adding the microcrystalline wax, the neutral oil and the glycerol into a high-speed shearing machine, heating to 50 ℃, stirring until the microcrystalline wax, the neutral oil and the glycerol are completely dissolved, adding the modified active agent and the oil-in-water type active agent, setting the stirring speed to be 1200rpm, carrying out high-speed shearing for 15min, vacuumizing to-0.1 MPa, and carrying out defoaming treatment for 20min to obtain the surfactant for leather fatliquoring.
Comparative example 1
This comparative example is a Gemini surfactant, supplied by Zhengzhou Yihe Fine Chemicals, inc.
Comparative example 2
The comparative example is a fat-liquoring agent SK-70 sold in the market, and is provided by Deshel chemical industry and chemical industry Co.
The surfactant prepared in examples 1 to 4 and provided in comparative example 1 was prepared into emulsion according to 1:5, and the emulsion state was tested by using 2000PAP type laser particle size analyzer and QBZY-1 type full automatic surface tensiometer, and the specific test data are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the surfactant prepared by the invention has a stable emulsification effect, the emulsion has fine particle size, the critical micelle concentration is 0.60-0.68g/L, the surface tension at the critical micelle concentration is only 25.4-29.1mN/m, the oleophylic property and the hydrophilic property are balanced, and the surface tension is obviously reduced.
Taking the surfactants prepared in examples 1-4, preparing the fatting agent with the same solid content according to the fatting agent provided in comparative example 2, using the sheep skin wet blue leather as a sample, using 8% of the fatting agent, using the same process to carry out fatting treatment, and carrying out the following performance tests on the treated leather:
testing the mechanical strength of the leather by adopting an AI-3000 type universal tensile machine;
testing the softness by adopting an HD-P807 leather softness meter;
specific test data are shown in table 2:
TABLE 2
As can be seen from the data in Table 2, the surfactant prepared by the method has a remarkable softening and strengthening effect on the wet-blue leather of the sheep leather when being applied to the fatliquor, wherein the softness of the leather is 7.46-8.15mm, and the leather is obviously superior to the existing high-quality fatliquor.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (6)
1. The surfactant for leather fatliquoring is characterized by comprising the following components in parts by weight:
40-60 parts of modified active agent, 18-25 parts of oil-in-water active agent, 4-8 parts of microcrystalline wax, 5-8 parts of neutral oil and 2-5 parts of glycerol;
the modified active agent is prepared by the following method:
step A1: mixing di-n-butylamine, acetone and triethylamine, heating to 50-55 ℃, adding epoxy chloropropane under a stirring state, performing reflux reaction for 30-40min, then adding a potassium tert-butoxide solution, performing reduced pressure rotary evaporation, washing with ice water, performing centrifugal liquid separation, and drying to obtain an epoxy intermediate;
step A2: mixing the epoxy intermediate, polyether diol with the average molecular weight of 600-1000, toluene and triphenylphosphine, heating to 100-110 ℃, stirring, refluxing and reacting for 60-80min, and carrying out reduced pressure rotary evaporation to obtain a bridging matrix;
step A3: mixing dioxane and deionized water, adding sulfamic acid and urea, stirring for dissolving, mixing with a bridging substrate, heating to 85-95 ℃, setting the stirring speed to 800-900rpm, stirring for reaction for 1.5-2h, dropwise adding a sodium hydroxide solution after the reaction until the pH value of a reaction system is 6.0, and carrying out reduced pressure rotary evaporation to remove the solvent to obtain a modified active agent;
the oil-in-water active agent is selected from Tween 80 and emulsifier BRIJ-721.
2. The surfactant for leather fatliquoring according to claim 1, wherein the amount ratio of di-n-butylamine, epichlorohydrin, acetone, triethylamine and potassium tert-butoxide is 1mol:1.2-1.4mol:100-120mL:1.6-2mL:0.1-0.2g.
3. A surfactant for greasing leather as claimed in claim 2 wherein the epoxy intermediate and polyether diol have a molar ratio of epoxy groups to hydroxyl groups of 1.
4. The surfactant for leather fatliquoring according to claim 3, wherein the amount ratio of the bridging substrate, sulfamic acid, urea, dioxane and deionized water is 100g:8.5-10g:1-1.2g:60-100mL:120-180mL.
5. The surfactant for leather fatliquoring according to claim 1, wherein the neutral oil is one selected from 32# -68# white oils.
6. The preparation method of the surfactant for leather fatliquoring according to claim 1, is characterized by comprising the following specific operations: mixing microcrystalline wax, neutral oil and glycerol, heating, stirring for dissolving, adding the modifying active agent and the oil-in-water active agent, shearing at high speed of 1200rpm for 10-20min, and performing vacuum defoaming treatment to obtain the surfactant for leather greasing.
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