CN115197361A - Acrylic ester polymer tanning agent and preparation method thereof - Google Patents
Acrylic ester polymer tanning agent and preparation method thereof Download PDFInfo
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- CN115197361A CN115197361A CN202210886599.8A CN202210886599A CN115197361A CN 115197361 A CN115197361 A CN 115197361A CN 202210886599 A CN202210886599 A CN 202210886599A CN 115197361 A CN115197361 A CN 115197361A
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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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
- 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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Abstract
The invention relates to the technical field of chemical tanning, and discloses an acrylic ester polymer tanning agent and a preparation method thereof, wherein the preparation method comprises the following steps: s1, under the participation of a first reaction solvent, dropwise adding cyanuric chloride into acetoacetoxy ethylene glycol methacrylate, and reacting to obtain a cyanuric chloride derivative; s2, dropwise adding an acrylate monomer and a vinyl sulfonate monomer into the cyanuric chloride derivative in the presence of a second reaction solvent to obtain a premix; and S3, under the participation of a third reaction solvent, dropwise adding an initiator and a molecular weight regulator into the premix to carry out solution polymerization, and then removing the reaction solvent to obtain the tanning agent. The invention prepares the acrylic ester polymer tanning agent without carboxyl, the tanning agent has a plurality of active binding points and is easy to combine with amino groups of the leather collagen fibers to form a cross-linked network structure. The shrinkage temperature can reach more than 90 ℃, and the tanning agent has good tanning effect. In addition, the polymer tanning agent can endow leather with good plumpness and elasticity.
Description
Technical Field
The invention relates to the technical field of chemical tanning, in particular to an acrylic ester polymer tanning agent and a preparation method thereof.
Background
Retanning is one of the most important processes in the production of leather. With the development of the leather-making industry, higher requirements are put forward on the color, quality, softness, fullness, elasticity, bleaching, light resistance and the like of leather. The traditional chrome tanning agent can not meet the requirements of high-grade leather. Therefore, retanning is generally regarded by domestic and foreign tanneries. This is because the repeated kneading can affect the properties of the leather in many ways, improving the look and feel and the inherent quality of the leather.
The principle of the acrylic acid polymer as a leather retanning agent is that carboxyl of acrylic acid is easily combined with chromium on chrome tanned leather to form a coordinate bond, so that the leather is endowed with plumpness and astringency. The acrylate polymer used for leather can be used as a filling material to endow the leather with plumpness. However, since the acrylate polymer has no binding functional group, it is easily removed by washing with water. Therefore, it is necessary to use acrylic acid or a monomer having a carboxyl group for copolymerization to achieve excellent adhesion.
Cyanuric chloride derivatives have been reported in a large number of patents and literatures as leather tanning agents, and mainly use the activity difference of different chlorine atoms on cyanuric chloride structures to prepare various types of derivatives. Wherein the first chlorine atom can generate substitution reaction with active hydrogen such as amino and the like at the temperature of 0-5 ℃ to prepare the derivative. The second chlorine atom can be substituted at 40-50 deg.C, and can be further reacted to obtain leather tanning agent.
< patent document >
Patent document CN106674141A
The patent uses cyanuric chloride first chlorine atom to react with active compound containing hydrophilic group to introduce sulfonic acid group or carboxylic acid group, then uses second chlorine atom to react with p-hydroxybenzaldehyde to prepare cyanuric chloride derivant. The derivative has aldehyde group and sulfonic group (carboxyl) and can be used for tanning softened acid leather, the tanning principle is that the aldehyde group and leather collagen form covalent bond combination, the sulfonic group (or carboxyl) and the amino group of the leather collagen form ionic bond combination, the shrinkage temperature of the tanned leather is up to 76 ℃, the leather belongs to single-point combination, and the leather does not reach a cross-linked structure.
Patent document No. two CN108085434A
The patent adopts polyamino compounds to prepare derivatives with cyanuric chloride at two ends by controlling the molar ratio of the polyamino compounds to the cyanuric chloride, and the tanning principle of the derivatives is that a covalent bond structure is formed by second chlorine atoms on the cyanuric chloride at two ends and collagen amino to achieve the purpose of crosslinking, so that the shrinkage temperature of tanned leather can be increased to 86 ℃. There is a drawback in that the cross-linking of the structure in a linear structure must be effected between two collagen fibers.
Moreover, the cyanuric chloride derivatives disclosed in the above patents are all small molecular compounds, and the tanned leather is thin.
Disclosure of Invention
< problems to be solved by the present invention >
The method is used for solving the problems that after the cyanuric chloride derivative is used as a leather tanning agent for tanning, the shrinkage temperature is not high enough, and the finished leather is shriveled.
< technical solution adopted in the present invention >
In view of the above-mentioned problems, an object of the present invention is to provide an acrylic acid ester polymer tanning agent and a method for producing the same. According to the invention, cyanuric chloride is introduced into an acrylate polymer structure to prepare the acrylate polymer tanning agent without carboxyl. The tanning agent has a plurality of active binding points and is easy to combine with amino groups of the leather collagen fibers to form a cross-linked network structure. The shrinkage temperature can reach more than 90 ℃, and the tanning agent has good tanning effect. In addition, the polymer tanning agent can endow leather with good plumpness and elasticity.
The specific contents are as follows:
the invention provides a preparation method of an acrylate polymer tanning agent, which comprises the following steps:
s1, under the participation of a first reaction solvent, dropwise adding cyanuric chloride and an acid-binding agent into acetoacetoxy ethylene glycol methacrylate, and reacting to obtain a cyanuric chloride derivative;
s2, dropwise adding an acrylate monomer and 2-acrylamide-2-methylpropanesulfonic acid into the cyanuric chloride derivative in the presence of a second reaction solvent to obtain a premix; and (3) dropwise adding an initiator and a molecular weight regulator into the premix in the presence of a third reaction solvent for solution polymerization, and removing the reaction solvent to obtain the tanning agent.
Secondly, the present invention provides an acrylic polymer tanning agent prepared by the above-mentioned preparation method.
< technical mechanism and advantageous effects of the present invention >
The cyanuric chloride derivative with carbon-carbon double bonds is prepared by reacting activated hydrogen between beta-dicarbonyl in an acetoacetoxy ethylene glycol methacrylate structure with cyanuric chloride.
The cyanuric chloride derivative prepared by the method is subjected to polymerization reaction with an acrylate monomer to prepare an acrylate polymer, so that the tanned leather is endowed with good fullness and elasticity and good tear strength.
The acrylic ester polymer tanning agent provided by the application has a plurality of cyanuric chloride structure sites, can form a multi-point cross-linking with skin collagen during tanning to form a cross-linked network structure, and achieves higher shrinkage temperature.
Drawings
FIG. 1 is a diagram showing the mechanism of action of various tanning agents with collagen;
FIG. 2 is a diagram of the action mechanism of acrylate polymer and collagen.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The invention provides a preparation method of an acrylic ester polymer tanning agent, which comprises the following steps:
s1, under the participation of a first reaction solvent, dropwise adding cyanuric chloride (TCT) and an acid-binding agent into acetoacetoxy ethylene glycol methacrylate, and reacting to obtain a cyanuric chloride derivative;
s2, dropwise adding an acrylate monomer and 2-acrylamide-2-methylpropanesulfonic acid into the cyanuric chloride derivative in the presence of a second reaction solvent to obtain a premix; and (3) dropwise adding an initiator and a molecular weight regulator into the premix in the presence of a third reaction solvent for solution polymerization, and removing the reaction solvent to obtain the tanning agent.
In the invention, in S1, the reaction temperature of the acetoacetoxy ethylene glycol methacrylate and the cyanuric chloride is 0-5 ℃, the dripping time is controlled to be 1-3 h, and after dripping is finished, the temperature is kept for 0.5-2 h.
In the invention, in S3, the temperature of the premix is raised to 25-30 ℃, the premix is dripped, stirring treatment is carried out during the dripping, the dripping time is controlled to 2-5 h, and the temperature is kept for 0.5-2 h after the dripping is finished.
In the invention, the molar ratio of cyanuric chloride, acetoacetoxy ethylene glycol methacrylate, acrylate monomer and 2-acrylamido-2-methylpropanesulfonic acid is 1 (2.0-2.2) to (4.26-10.17) to (1.98-2.15).
In the invention, the addition amounts of acetoacetoxy ethylene glycol methacrylate, cyanuric chloride, acrylate monomer and vinyl sulfonate monomer are taken as the total mass, and the amount of the initiator accounts for 10-20% of the total mass; and/or the dosage of the molecular weight regulator accounts for 2-5% of the total mass.
In the present invention, the acrylate monomer includes at least one of Butyl Acrylate (BA), ethyl methacrylate (me), and Ethyl Acrylate (EA).
In the invention, the initiator is an oxidation-reduction initiator and consists of dibenzoyl peroxide and N, N-dimethylaniline; and/or the molecular weight regulator is dodecyl mercaptan.
In the invention, the first reaction solvent is acetone; the second reaction solvent and the third reaction solvent are both N, N-dimethylacetamide.
In the invention, in S1, the acid-binding agent is triethylamine or sodium hydroxide, and the dosage of the acid-binding agent is 1.2-1.5 times of the molar weight of cyanuric chloride;
when the acid-binding agent is used, the acid-binding agent is prepared into a solution, specifically a triethylamine acetone solution or a sodium hydroxide aqueous solution.
In the invention, in S1, acetoacetoxy ethylene glycol methacrylate and cyanuric chloride are dissolved in a first reaction solvent to obtain corresponding solution, and then the reaction is carried out;
the molar concentration of the acetoacetoxy glycol methacrylate solution is 1.17-2.34 mmol/mL;
and/or the presence of a gas in the gas,
in S2, the addition amounts of acetoacetoxy ethylene glycol methacrylate, cyanuric chloride, an acrylate monomer and 2-acrylamido-2-methylpropanesulfonic acid are taken as the total mass, and the addition amount of the second reaction solvent accounts for 0.79-1.16 times of the total mass;
and/or the presence of a gas in the gas,
and in S3, dissolving the initiator in a third reaction solvent to obtain a corresponding solution, and then carrying out reaction.
The molar concentration ranges of the dibenzoyl peroxide solution and the N, N-dimethylaniline solution are 1.03-1.65 mmol/mL and 2.06-3.30 mmol/mL respectively.
Secondly, the present invention provides an acrylic polymer tanning agent obtained by the above-mentioned production method.
< synthetic principle route >
The synthesis route of the polyacrylic acid polymer tanning agent provided by the previous step is as follows:
wherein a, b, c and d are integers, and n is a positive integer.
< mechanism of action of tanning agent and leather collagen fiber >
The mechanism of action of tanning agents with collagen in the prior art is shown in figure 1;
the mechanism of action of polyacrylic acid polymer tanning agent with collagen provided by the present application is shown in figure 2. R shown in fig. 2, which is a repeating unit structure. The method specifically comprises the following steps:
fig. 1 illustrates the range of leather shrinkage temperature increase relative to the hide shrinkage temperature increase after tanning with various tanning agents. In view of the resistance to wet heat temperatures of the hides and the leathers obtained by the various tanning processes available: hide 65 ℃, oil-tanned leather 60-70 ℃, vegetable-tanned leather 75-85 ℃, formaldehyde-tanned leather 80-85 ℃, aluminum-tanned leather 70-75 ℃, zirconium-tanned leather 90-95 ℃, chrome-tanned leather more than 100 ℃ (Chen Wuyong, li Guoying. Tanning chemistry [ M ]. Third edition. Beijing: china light industry Press, 2011. The chrome tanning can form a multi-point crosslinking network structure from the principle, so that the shrinkage temperature of the finished leather is high.
Based on the above, as can be seen from fig. 2, the acrylic ester polymer tanning agent prepared by the method is similar to a chrome tanning principle, and has multiple active chain segments, so that a cross-linked network structure is formed between fibers after tanning, and the purpose of increasing the shrinkage temperature is achieved.
< example >
Example 1
(1) 156.82g (0.7321 mol) AAEM and 157mL acetone are added into the reaction vessel to mix, 337.50g (containing 0.3660mol TCT) TCT acetone saturated solution is slowly dropped into the reaction vessel while 89mL triethylamine acetone solution with the molar concentration of 4.94mmol/mL is dropped into the reaction vessel. The dripping time is controlled to be 2.5h, and the temperature is kept for 1h after the dripping is finished.
(2) 200g (1.5604 mol) BA and 150g (0.7238 mol) AMPS are added to step (1), and 450mLDMAc is supplemented. Stirring was started, and while controlling the temperature at 25 ℃, 144mL of a DMAc solution having a molar concentration of 1.65mmol/mL of BPO, 72mL of a DMAc solution having a molar concentration of 3.30mmol/mL of DMA, and 57mL of a DMAc solution having a molar concentration of 0.99mmol/mL of dodecanethiol were added dropwise to carry out solution polymerization. The dropping time is controlled at 3h, after the dropping is finished, the solution is subjected to spray drying after the temperature is kept at 25 ℃ for 1h to remove the solvent, so that a white powdery product is obtained, and the weight average molecular weight is determined to be 4529.
Example 2
(1) 153.34g (0.7158 mol) AAEM and 157mL acetone are added into a reaction vessel to be mixed, the temperature is controlled at 0-5 ℃, 300g (containing 0.3254mol TCT) TCT acetone saturated solution is slowly dripped, and 79mL triethylamine acetone solution with the molar concentration of 4.94mmol/mL is dripped at the same time. The dripping time is controlled to be 2.0h, and the temperature is kept for 1h after the dripping is finished.
(2) 190g (1.4824 mol) BA and 140g (0.6755 mol) AMPS are added into the step (1), and 420mLDMAc is added. Stirring was started, and while controlling the temperature at 30 ℃, solution polymerization was carried out by dropwise adding 136mL of a DMAc solution having a molar concentration of 1.65mmol/mL of BPO, 68mL of a DMAc solution having a molar concentration of 3.30mmol/mL of DMA, and 54mL of a DMAc solution having a molar concentration of 0.99mmol/mL of dodecanethiol, respectively. The dropping time is controlled to be 3h, after the dropping is finished, the solution is subjected to spray drying after the temperature is kept at 30 ℃ for 2h to remove the solvent, so that a white powdery product is obtained, and the weight average molecular weight is determined to be 6953.
Example 3
(1) 156.82g (0.7321 mol) AAEM and 157mL acetone are added into a reaction vessel to be mixed, the temperature is controlled at 0-5 ℃, 337.5g (containing 0.3660mol TCT) TCT acetone saturated solution is slowly dripped, and 96mL triethylamine acetone solution with the molar concentration of 4.94mmol/mL is dripped at the same time. The dripping time is controlled to be 3.0h, and the temperature is kept for 1h after dripping is finished.
(2) 200g (1.5604 mol) BA and 150g (0.7238 mol) AMPS are added into the step (1), and 450mLDMAc is supplemented. The stirring was started, and while controlling the temperature at 25 ℃, 230mL of a DMAc solution with a molar concentration of 1.03mmol/mL BPO, 115mL of a DMAc solution with a molar concentration of 2.06mmol/mL DMA, and 57mL of a DMAc solution with a molar concentration of 0.99mmol/mL dodecanethiol were added dropwise, respectively, to carry out solution polymerization. The dropping time is controlled to be 3h, after the dropping is finished, the temperature is kept at 25 ℃ for 1h, then the solvent is removed by spray drying to obtain a white powdery product, and the weight average molecular weight is measured to be 5862.
Example 4
(1) 172.51g (0.8053 mol) AAEM and 157mL acetone are added into a reaction vessel to be mixed, the temperature is controlled at 0-5 ℃, 337.5g (containing 0.3660mol TCT) TCT acetone saturated solution is slowly dripped, and 112mL triethylamine acetone solution with the molar concentration of 4.94mmol/mL is dripped at the same time. The dripping time is controlled to be 3.0h, and the temperature is kept for 1h after the dripping is finished.
(2) 200g (1.5604 mol) BA and 150g (0.7238 mol) AMPS are added to step (1), and 450mLDMAc is supplemented. While stirring was started and the temperature was controlled at 25 ℃, 189mL of a DMAc solution having a molar concentration of 1.03mmol/mL of BPO, 118mL of a DMAc solution having a molar concentration of 2.06mmol/mL of DMA and 147mL of a DMAc solution having a molar concentration of 0.99mmol/mL of dodecanethiol were added dropwise to carry out solution polymerization. The dropping time is controlled at 3h, after the dropping is finished, the temperature is kept at 25 ℃ for 1h, then the solvent is removed by spray drying to obtain a white powder product, and the weight average molecular weight is determined to be 7635.
Example 5
(1) 63.89g (0.2982 mol) of AAEM and 67mL of acetone are added into a reaction vessel, mixed, slowly dropped with 125.0g (containing 0.1356mol of TCT) of acetone saturated solution of TCT at the temperature of 0-5 ℃, and simultaneously dropped with 41mL of sodium hydroxide aqueous solution with the molar concentration of 4.94 mol/mL. The dripping time is controlled to be 1.5h, and the temperature is kept for 1h after the dripping is finished.
(2) Adding 100g (0.7802 mol) BA and 56g (0.2702 mol) AMPS into the step (1), and supplementing 168mLDMAc. Stirring was started, and while controlling the temperature at 25 ℃, solution polymerization was carried out by dropwise adding 98mL of a DMAc solution having a molar concentration of 1.38mmol/mL of BPO, 49mL of a DMAc solution having a molar concentration of 2.75mmol/mL of DMA, and 61mL of a DMAc solution having a molar concentration of 1.24mmol/mL of dodecanethiol. The dropping time is controlled to be 3h, after the dropping is finished, the temperature is kept at 25 ℃ for 1h, then the solvent is removed by spray drying to obtain a white powdery product, and the weight average molecular weight is measured to be 5064.
Example 6
(1) 67.38g (0.3145 mol) of AAEM and 67mL of acetone are added into a reaction vessel to be mixed, the temperature is controlled at 0-5 ℃, 145.0g (containing 0.1573mol of TCT) of TCT acetone saturated solution is slowly dripped, and 38mL of triethylamine acetone solution with the molar concentration of 4.94mmol/mL is dripped at the same time. The dripping time is controlled to be 1.5h, and the temperature is kept for 1h after the dripping is finished.
(2) 200g (1.5604 mol) BA, 67.5g (0.3257 mol) AMPS were added to step (1), and 202.5mL DMAC was added. Stirring was started, and while controlling the temperature at 25 ℃, 91mL of a DMAc solution having a molar concentration of 1.65mmol/mL of BPO, 46mL of a DMAc solution having a molar concentration of 3.30mmol/mL of DMA, and 36mL of a DMAc solution having a molar concentration of 0.99mmol/mL of dodecanethiol were added dropwise to carry out solution polymerization. The dropping time is controlled to be 3h, after the dropping is finished, the temperature is kept at 25 ℃ for 1h, then the solvent is removed by spray drying to obtain a white powdery product, and the weight average molecular weight is determined to be 4921.
Example 7
(1) 74.11g (0.3460 mol) AAEM and 74mL acetone are added into a reaction vessel to be mixed, the temperature is controlled at 0-5 ℃, 145g (containing 0.1573mol TCT) TCT acetone saturated solution is slowly dripped, and 44mL triethylamine acetone solution with the molar concentration of 4.94mmol/mL is dripped at the same time. The dripping time is controlled to be 1.5h, and the temperature is kept for 1h after the dripping is finished.
(2) 205g (1.5994 mol) BA, 70g (0.3378 mol) AMPS were added to step (1), and 210mLDMAc was added. Stirring was started, and while controlling the temperature at 25 ℃, 95mL of a DMAc solution having a molar concentration of 1.65mmol/mL of BPO, 47mL of a DMAc solution having a molar concentration of 3.30mmol/mL of DMA, and 76mL of a DMAc solution having a molar concentration of 0.99mmol/mL of dodecanethiol were added dropwise to carry out solution polymerization. The dropping time is controlled to be 3h, after the dropping is finished, the temperature is kept at 30 ℃ for 1h, then the solvent is removed by spray drying to obtain a white powdery product, and the weight average molecular weight is 6875.
Example 8
(1) 70.74.g (0.3302 mol) of AAEM and 71mL of acetone are added into a reaction vessel to be mixed, 145g (containing 0.1573mol TCT) of TCT acetone saturated solution is slowly dripped while 38.2mL of triethylamine acetone solution with the molar concentration of 4.94mmol/mL is dripped at the temperature of 0-5 ℃. The dripping time is controlled to be 1.5h, and the temperature is kept for 1h after the dripping is finished.
(2) Adding 205g (1.5994 mol) BA and 70g (0.3378 mol) AMPS into the step (1), and supplementing 210mLDMAc. Stirring is started, the temperature is controlled at 25 ℃, and at the same time, 150mL of DMAc solution with the molar concentration of 1.03mmol/mL BPO, 75mL of DMAc solution with the molar concentration of 2.06mmol/mL DMA and 94mL of DMAc solution with the molar concentration of 0.99mmol/mL dodecanethiol are respectively added dropwise for solution polymerization. The dropping time is controlled to be 4h, after the dropping is finished, the temperature is kept at 25 ℃ for 1h, then the solvent is removed by spray drying to obtain a white powdery product, and the weight average molecular weight is measured to be 8531.
< test example >
The sheep skin was tested for its pelts in examples 1-8 and comparative example 1 (Granofin F-90, starter).
The experimental treatment procedure was as follows: and (3) taking the naked sheepskin for tanning after soaking → liming → deliming → softening, wherein the using amount of the used substances is calculated according to the weight of the hide. The tanning process is shown in table 1 below.
TABLE 1 tanning Process flow
The results of the experiments after treatment by the process described in table 1 are shown in table 2.
TABLE 2 tanning results
| Tanning agent | Shrinkage temperature/. Degree.C | Hand feeling | Tensile strength/MPa | Tear Strength/N.mm-1 |
| Example 1 | 95 | Full and elastic | 286.32 | 81.58 |
| Example 2 | 95 | Full and elastic | 297.36 | 82.54 |
| Example 3 | 90 | Full and elastic | 256.25 | 78.49 |
| Example 4 | 98 | Full and elastic | 380.28 | 86.68 |
| Example 5 | 93 | Full and elastic | 276.45 | 79.35 |
| Example 6 | 93 | Full and elastic | 272.22 | 78.96 |
| Example 7 | 91 | Full and elastic | 260.37 | 80.65 |
| Example 8 | 96 | Full and elastic | 301.12 | 83.79 |
| Comparative example 1 | 77 | Soft and shriveled | 305.8 | 53.64 |
As can be seen from the data in Table 2, the organic tanning agent prepared by the method can be used for directly tanning a naked leather to prepare leather, so that the tanned leather has full and elastic handfeel.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the acrylic ester polymer tanning agent is characterized by comprising the following steps:
s1, under the participation of a first reaction solvent, dropwise adding cyanuric chloride and an acid-binding agent into acetoacetoxy ethylene glycol methacrylate, and reacting to obtain a cyanuric chloride derivative;
s2, in the presence of a second reaction solvent, dropwise adding an acrylate monomer and 2-acrylamido-2-methylpropanesulfonic acid to the cyanuric chloride derivative to obtain a premix; and (3) dropwise adding an initiator and a molecular weight regulator into the premix in the presence of a third reaction solvent to carry out solution polymerization, and then removing the reaction solvent to obtain the tanning agent.
2. The method for producing an acrylic polymer tanning agent according to claim 1, wherein,
in S1, the reaction temperature of the acetoacetoxy ethylene glycol methacrylate and cyanuric chloride is 0-5 ℃, the dripping time is controlled to be 1-3 h, and after dripping is finished, the temperature is kept for 0.5-2 h.
3. The method for producing an acrylic polymer tanning agent according to claim 1, wherein,
and S2, heating the premix to 25-30 ℃, dropwise adding, controlling the dropwise adding time to be 2-5 h, and keeping the temperature for 0.5-2 h after dropwise adding.
4. The method for producing an acrylic polymer tanning agent according to any of claims 1 to 3, characterized in that,
the molar ratio of cyanuric chloride to acetoacetoxy ethylene glycol methacrylate to acrylate monomer to 2-acrylamido-2-methylpropanesulfonic acid is 1 (2.0-2.2) to (4.26-10.17) to (1.98-2.15).
5. The method for preparing the acrylic ester polymer tanning agent according to claim 1, wherein the addition amount of acetoacetoxy ethylene glycol methacrylate, cyanuric chloride, an acrylic ester monomer and a vinyl sulfonate monomer is taken as the total mass, and the amount of an initiator accounts for 10-20% of the total mass; and/or the dosage of the molecular weight regulator accounts for 2-5% of the total mass.
6. The method for producing an acrylic polymer tanning agent according to any of claims 1 to 3, characterized in that in S2, the reaction solvent is removed by spray drying.
7. The method for preparing an acrylic polymer tanning agent according to any one of claims 1 to 3, characterized in that the initiator is an oxidation-reduction initiator consisting of dibenzoyl peroxide and N, N-xylidine; and/or the molecular weight regulator is dodecyl mercaptan.
8. The method for producing an acrylic polymer tanning agent according to claim 1, wherein in S1, the first reaction solvent is acetone;
and/or the presence of a gas in the gas,
in the S1, an acid-binding agent is triethylamine or sodium hydroxide, and the using amount of the acid-binding agent is 1.2-1.5 times of the molar weight of cyanuric chloride;
and/or the presence of a gas in the gas,
the second reaction solvent and the third reaction solvent are both N, N-dimethylacetamide or isopropanol.
9. The method for producing an acrylate-based polymer tanning agent according to claim 1 or 8,
in S1, dissolving acetoacetoxy ethylene glycol methacrylate and cyanuric chloride in a first reaction solvent to obtain corresponding solution, and reacting;
the molar concentration of the acetoacetoxy glycol methacrylate solution is 1.17-2.34 mmol/mL;
and/or the presence of a gas in the gas,
in S2, the addition amounts of acetoacetoxy ethylene glycol methacrylate, cyanuric chloride, an acrylate monomer and a vinyl sulfonate monomer are taken as the total mass, and the addition amount of the second reaction solvent accounts for 0.79-1.16 times of the total mass;
and/or the presence of a gas in the gas,
and in S3, dissolving the initiator in a third reaction solvent to obtain a corresponding solution, and then carrying out reaction.
10. An acrylic polymer tanning agent obtained by the preparation method of any one of claims 1 to 9.
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| US20050125906A1 (en) * | 2002-05-07 | 2005-06-16 | Basf Aktiengesellschaft | Tanning agent and curing agent based on dialdehydes |
| WO2009105963A1 (en) * | 2008-02-26 | 2009-09-03 | Rhodia-Hengchang (Zhangjiagang) Specialty Chemical Co., Ltd. | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| CN111363864A (en) * | 2018-12-26 | 2020-07-03 | 温州大学 | Nonmetal cation tanning agent and preparation method thereof |
| CN111979364A (en) * | 2020-09-09 | 2020-11-24 | 四川亭江新材料股份有限公司 | Low-molecular-weight aqueous polyurethane type leather organic tanning agent and preparation method and application thereof |
| CN114479061A (en) * | 2022-01-21 | 2022-05-13 | 四川大学 | Polyether amine chlorotriazine telechelic polymer tanning agent, and preparation method and application thereof |
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| US20050125906A1 (en) * | 2002-05-07 | 2005-06-16 | Basf Aktiengesellschaft | Tanning agent and curing agent based on dialdehydes |
| WO2009105963A1 (en) * | 2008-02-26 | 2009-09-03 | Rhodia-Hengchang (Zhangjiagang) Specialty Chemical Co., Ltd. | Poly hydroxyl alkyl phosphine-organic silicon tanning agent, its preparation and application in fur tanning |
| CN111363864A (en) * | 2018-12-26 | 2020-07-03 | 温州大学 | Nonmetal cation tanning agent and preparation method thereof |
| CN111979364A (en) * | 2020-09-09 | 2020-11-24 | 四川亭江新材料股份有限公司 | Low-molecular-weight aqueous polyurethane type leather organic tanning agent and preparation method and application thereof |
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