CN107937636B - Silicon-containing retanning fatliquor and preparation method thereof - Google Patents
Silicon-containing retanning fatliquor and preparation method thereof Download PDFInfo
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- CN107937636B CN107937636B CN201711210173.6A CN201711210173A CN107937636B CN 107937636 B CN107937636 B CN 107937636B CN 201711210173 A CN201711210173 A CN 201711210173A CN 107937636 B CN107937636 B CN 107937636B
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- silicon
- containing polymer
- retanning fatliquor
- fatliquor
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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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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a silicon-containing retanning fatliquor and a preparation method thereof, belonging to the technical field of leather. Mainly comprises a silicon-containing polymer, a neutralizer, an emulsifier and water. The preparation method comprises the following steps: adding the silicon-containing polymer, the neutralizer and the emulsifier into a reaction kettle, mixing at the temperature of 50-70 ℃ and the stirring speed of 130-170r/min, adding water, continuously dispersing for 0.8-1.2h, and cooling to obtain the silicon-containing retanning fatliquor. The silicon-containing retanning fatliquor prepared by the method can endow leather with good flexibility and excellent waterproof performance.
Description
Technical Field
The invention relates to the technical field of leather, in particular to a silicon-containing retanning fatliquor and a preparation method thereof.
Background
The polymer retanning fatliquor has the retanning filling function and the lubricating fatliquoring function, and can theoretically replace the fatliquoring agent and the retanning agent.
The hydrophobic side chain of the existing polymer retanning fatliquor on the market is generally a long hydrocarbon chain, the main chain is formed by C-C bonds, and the fatliquor has a certain fatliquor effect, but the softness of a leather blank after fatliquor is not enough, so that the traditional fatliquor cannot be completely replaced, and the waterproof effect is limited.
Disclosure of Invention
The invention aims to provide a silicon-containing retanning fatliquor, which uses a silicon-containing polymer, so that the obtained silicon-containing retanning fatliquor can enable leather to have good softness and excellent waterproof performance.
The invention also aims to provide a preparation method of the silicon-containing retanning fatliquor, which has the advantages of easy equipment acquisition, simple method and convenient operation.
The invention is realized by adopting the following technical scheme:
a silicon-containing retanning fatliquor comprises the following components in percentage by weight: 15-30 wt% of silicon-containing polymer, 0-30 wt% of neutralizing agent, 0-20 wt% of emulsifier and the balance of water.
A preparation method of a silicon-containing retanning fatting agent comprises the steps of adding a silicon-containing polymer, a neutralizing agent and an emulsifying agent into a reaction kettle, mixing at the temperature of 50-70 ℃ and the stirring speed of 130-.
The weight percentages are as follows: 15-30 wt% of silicon-containing polymer, 0-30 wt% of neutralizing agent, 0-20 wt% of emulsifier and the balance of water.
The silicon-containing retanning fatliquor provided by the preferred embodiment of the invention has the beneficial effects that: the silicon-containing polymer in the silicon-containing retanning fatliquor uses siloxane to replace a long carbon chain of the traditional retanning fatliquor, and an organosilicon main chain has long Si-O bond, large bond angle and small side chain steric hindrance, so that Si-O-Si is easy to rotate, and the leather is endowed with good softness due to the high-compliance state of molecules; because the silicon atom is connected with two methyl groups, the steric effect of the methyl groups can endow leather with excellent waterproof effect, and particularly, when the redundant carboxyl groups of the polymer fatliquor combined in the leather are sealed by polyvalent metal salt, the waterproof performance is more outstanding. The addition of the neutralizing agent and the emulsifying agent is favorable for better dispersion of the silicon-containing polymer in water and storage stability of the silicon-containing retanning fatliquor.
The preparation method of the silicon-containing retanning fatliquor provided by the invention has the beneficial effects that: stirring in a reaction kettle to uniformly disperse the silicon-containing polymer, the neutralizer and the emulsifier, wherein the silicon-containing retanning fatting agent is more uniformly dispersed and used in the fatting process of the leather, so that the effect on the leather is better, and the softness and the waterproof performance of the leather can be better improved.
Detailed Description
The hydrophobic side chain of the existing polymer retanning fatliquor on the market is generally a long hydrocarbon chain, the main chain is formed by C-C bonds, and the fatliquor has a certain fatliquor effect, but the softness of a leather blank after fatliquor is not enough, so that the traditional fatliquor cannot be completely replaced, and the waterproof effect is limited.
The inventors have found that the use of a silicon-containing polymer as a retanning fatliquor ameliorates the above-mentioned disadvantages.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in 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 not indicated by the manufacturer, and are all conventional products available commercially.
The silicon-containing retanning fatliquor and the preparation method thereof according to the embodiment of the invention are specifically described below.
The silicon-containing retanning fatliquor comprises the following components in percentage by weight: 15-30 wt% of silicon-containing polymer, 0-30 wt% of neutralizing agent, 0-20 wt% of emulsifier and the balance of water.
Wherein: comprisesThe side chain of the silicon polymer contains siloxane, and the basic structural unit is-Si (CH)3)2The O-silicon-containing polymer is a long carbon chain which uses siloxane to replace the traditional retanning fatliquor, the Si-O bond of the main chain of the organic silicon is long, the bond angle is large, and the steric hindrance of the side chain is small, so that the Si-O-Si can easily rotate, and the leather can be endowed with good softness due to the high-compliance state of the molecules; because the silicon atom is connected with two methyl groups, the steric effect of the methyl groups can endow leather with excellent waterproof effect, and particularly, when the redundant carboxyl groups of the polymer fatliquor combined in the leather are sealed by polyvalent metal salt, the waterproof performance is more outstanding.
Preferably, the side chain content of the silicon-containing polymer is 5-50 wt%, the side chain molecular weight of the silicon-containing polymer is 200-50000, the carboxyl content of the silicon-containing polymer is 1-30 wt%, and the molecular weight of the silicon-containing polymer is 500-50000.
The silicone enables the silicon-containing retanning fatliquor to improve the waterproof effect of leather, and the side chain content of the silicon-containing polymer is too high, namely the silicone content is too high, so that the storage stability and the fatliquoring permeability of the product are influenced, and the softness is not enough; if the side chain content of the silicon-containing polymer is too small, that is, if the siloxane content is too small, the softness and water-repellent effect are poor. The side chain molecular weight of the silicon-containing polymer is too large, namely the molecular weight of siloxane is too high, so that the fat penetration performance is influenced, and the softness is insufficient; if the molecular weight of the side chain of the silicon-containing polymer is too small, that is, if the molecular weight of siloxane is too low, softness and water-repellent effect are poor.
The carboxyl enables the silicon-containing retanning fatliquor to improve the filling effect of leather, the carboxyl content is too low, the storage stability of the product is not good, and the filling effect of the leather after use is not obvious; if the carboxyl group content is too high, the filling property is too high and the softness of the leather is not good. The leather softness is poor due to the influence of the too high molecular weight of the silicon-containing polymer on the permeability; if the molecular weight of the silicon-containing polymer is too low, the water-repellent effect is not satisfactory.
Therefore, by controlling the carboxyl content and the molecular weight of the silicon-containing polymer, and the content and the molecular weight of siloxane, the leather has better waterproof performance and softness after the silicon-containing retanning fatliquor is used on the leather, and can better meet the requirements of consumers.
The main chain of the silicon-containing polymer is formed by self polymerization of at least one unsaturated monomer of methacrylic acid, acrylic acid, maleic anhydride, maleic acid and itaconic acid or copolymerization of a plurality of unsaturated monomers. The main chain of the silicon-containing polymer also comprises one or more of ethyl acrylate, butyl acrylate, hexyl acrylate and octyl acrylate, namely the main chain of the silicon-containing polymer can be obtained by copolymerizing one or more of methacrylic acid, acrylic acid, maleic anhydride, maleic acid and itaconic acid with one or more of ethyl acrylate, butyl acrylate, hexyl acrylate and octyl acrylate.
In the invention, the carboxyl on the main chain and the epoxy-terminated silicone oil are subjected to ring-opening reaction to obtain the silicon-containing polymer. Namely, the epoxy functional group of the epoxy-terminated silicone oil is more active and is easy to react with the carboxyl on the main chain to form a siloxane side chain and form a silicon-containing polymer, wherein part of the carboxyl is reserved in the silicon-containing polymer.
In the invention, the amino-terminated silicone oil and the anhydride in the maleic anhydride are subjected to amidation reaction to introduce siloxane in the amino-terminated silicone oil to a polymer side chain, and simultaneously generate carboxyl to form a silicon-containing polymer.
In the present invention, the preparation of the silicon-containing polymer is not limited to the above-mentioned method, as long as the silicon-containing polymer can be prepared, and the method falls within the scope of the present invention.
The neutralizer can perform acid-base neutralization reaction with carboxyl in the silicon-containing polymer, adjust the pH value of the silicon-containing retanning fatliquor, ionize the carboxyl and increase the emulsifying property of the silicon-containing retanning fatliquor. The neutralizer is one of sodium hydroxide solution, potassium hydroxide solution, ammonia water solution, ethanolamine solution, diethanolamine solution and triethanolamine solution, and has a concentration of 20-30 wt%. The alkali salt can ionize carboxyl and improve the emulsifying effect of the silicon-containing retanning fatliquor.
The emulsifier can improve the emulsifying and penetrating capacity of the silicon-containing retanning fatliquor, is a surfactant, forms a film or an electric double layer when the emulsifier is dispersed on the surface of a dispersoid, can enable a dispersed phase to carry charges, can prevent small droplets of the dispersed phase from mutually coagulating, enables the formed emulsion to be relatively stable, and avoids the finally obtained silicon-containing retanning fatliquor from being layered. Meanwhile, the leather retanning fatliquor has hydrophilic and oleophylic characteristics, so that the components of the silicon-containing retanning fatliquor are mixed more uniformly and can be more easily permeated into leather, and the fatliquoring effect of the silicon-containing retanning fatliquor is better.
The present invention is not particularly limited in kind and source of the emulsifier, and may be commercially available by using an emulsifier well known to those skilled in the art. In the present invention, the emulsifier is selected from at least one of isomeric tridecanol polyoxyethylene ether (TO series) and fatty alcohol polyoxyethylene ether (AEO series). Can improve the emulsifying and penetrating abilities of the silicon-containing retanning fatting agent.
The effective solid content of the silicon-containing retanning fatliquor is 25-35%, and the pH value is 6.5-8. The leather has better flexibility and excellent waterproof performance.
The preparation method of the silicon-containing retanning fatliquor comprises the steps of adding a silicon-containing polymer, a neutralizing agent and an emulsifying agent into a reaction kettle, mixing at the temperature of 50-70 ℃ and the stirring speed of 130-.
Wherein: according to the percentage, 15-30 wt% of silicon-containing polymer, 0-30 wt% of neutralizing agent, 0-20 wt% of emulsifying agent and the balance of water.
The reaction is carried out in the reaction kettle, the equipment is simple and easy to obtain, the manufacturing cost can be greatly reduced, and the batch production can be realized.
The reaction is carried out at 50-70 ℃, the molecular movement speed is high within the range, and the neutralizer can ionize carboxyl of the silicon-containing polymer and improve the emulsification effect of the silicon-containing retanning fatliquor. Meanwhile, the three substances are easy to mix, so that the three substances are more uniformly distributed when being used on the leather, and the leather has good flexibility and excellent waterproof effect. The temperature is not too high, the silicon-containing polymer and the emulsifier do not have chemical reaction, the chemical property of the silicon-containing polymer and the emulsifier is kept, and the silicon-containing retanning fatliquor can enable leather to have good softness and excellent waterproof performance.
Under the stirring speed of 130-170r/min, water is added for dispersing for a certain time, so that the components can be mixed more uniformly.
Preferably, water is slowly added, and the components of the silicon-containing retanning fatliquor have better dispersion effect. And after the water is added, the dispersion is continued for a period of time, so that the dispersion of each component is more uniform.
Wherein the silicon-containing polymer is introduced to the side chain of the polymer by a ring-opening reaction of the terminal epoxy silicone oil with the carboxyl group on the main chain or an amidation reaction of the terminal amino silicone oil with the acid anhydride on the main chain.
Example 1
Adding 30 wt% of silicon-containing polymer into a reaction kettle, adding 70 wt% of water at the stirring speed of 130r/min at 50 ℃, continuing to disperse for 0.8h, and cooling to obtain the silicon-containing retanning fatliquor.
Example 2
Adding 15 wt% of silicon-containing polymer and 20 wt% of fatty alcohol-polyoxyethylene ether into a reaction kettle, adding 65 wt% of water at the temperature of 70 ℃ and the stirring speed of 170r/min, continuing dispersing for 1.2h, and cooling to obtain the silicon-containing retanning fatliquor.
Example 3
Adding 20 wt% of silicon-containing polymer (the carboxyl content of the silicon-containing polymer is 30 wt%, the molecular weight of the silicon-containing polymer is 50000, the side chain content of the silicon-containing polymer is 50 wt%, the side chain molecular weight of the silicon-containing polymer is 3000), 6 wt% of isomeric tridecanol polyoxyethylene ether and 30 wt% of ammonia water solution (the concentration is 30 wt%) into a reaction kettle, adding 44 wt% of water at the stirring speed of 150r/min at the temperature of 60 ℃, continuing dispersing for 1h, and cooling to obtain the silicon-containing retanning fatliquor.
Example 4
Adding 24.4 wt% of silicon-containing polymer (the carboxyl content of the silicon-containing polymer is 1 wt%, the molecular weight of the silicon-containing polymer is 500, the side chain content of the silicon-containing polymer is 5 wt%, the side chain molecular weight of the silicon-containing polymer is 200), 5 wt% of isomeric tridecanol polyoxyethylene ether and 1 wt% of ammonia water solution (the concentration is 21 wt%) into a reaction kettle, adding 69.6 wt% of water at the stirring speed of 150r/min at the temperature of 60 ℃, continuing dispersing for 1h, and cooling to obtain the silicon-containing retanning fatliquor.
Example 5
Adding 24.4 wt% of silicon-containing polymer (the carboxyl content of the silicon-containing polymer is 10 wt%, the molecular weight of the silicon-containing polymer is 5000, the side chain content of the silicon-containing polymer is 15 wt%, the side chain molecular weight of the silicon-containing polymer is 300), 5 wt% of isomeric tridecanol polyoxyethylene ether and 3 wt% of ammonia water solution (the concentration is 20 wt%) into a reaction kettle, adding 67.6 wt% of water at the stirring speed of 150r/min at the temperature of 60 ℃, continuing dispersing for 1h, and cooling to obtain the silicon-containing retanning fatliquor.
Example 6
Adding 22.5 wt% of silicon-containing polymer (the carboxyl content of the silicon-containing polymer is 15 wt%, the molecular weight of the silicon-containing polymer is 8000, the side chain content of the silicon-containing polymer is 25 wt%, the side chain molecular weight of the silicon-containing polymer is 600), 2 wt% of fatty alcohol-polyoxyethylene ether and 18.3 wt% of diethanolamine solution (the concentration is 30 wt%) into a reaction kettle, adding 57.2 wt% of water at the stirring speed of 150r/min at the temperature of 60 ℃, continuing dispersing for 1h, and cooling to obtain the silicon-containing retanning fatliquor.
Examples of the experiments
The silicon-containing retanning fatliquor prepared in examples 1-6 was applied to the leather of a cow leather upper for retanning fatliquor with a commercial retanning fatliquor in an effective amount of 4 wt% of the wet weight, the leather treated with the silicon-containing retanning fatliquor of examples 1-6 gave examples 1-6, the leather treated with the commercial retanning fatliquor gave commercial products, and the application comparisons gave the following table 1:
TABLE 1 leather surface fatliquoring
It can be seen from table 1 that the silicon-containing retanning fatliquor of examples 1-6 of the present invention is superior to the same products on the market, and the silicon-containing retanning fatliquor makes the leather more flexible and has very good absorption and penetration capacity.
The silicon-containing retanning fatliquor prepared in examples 1-6 was applied to the leather of a cow leather upper for retanning fatliquor with a commercial retanning fatliquor in an effective amount of 4 wt% of the wet weight, the leather treated with the silicon-containing retanning fatliquor of examples 1-6 gave examples 1-6, the leather treated with the commercial retanning fatliquor gave commercial products, and the application comparisons gave the following table 2:
TABLE 2 leather surface waterproofing
As can be seen from Table 2, the silicon-containing retanning fatliquor of examples 1-6 of the present invention is superior to the similar products in the market, and the silicon-containing retanning fatliquor makes the leather have better waterproof effect and can better meet the requirements of consumers.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. 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.
Claims (6)
1. The silicon-containing retanning fatliquor is characterized by comprising the following components in percentage by weight: 15-30 wt% of silicon-containing polymer, 0-30 wt% of neutralizing agent, 0-20 wt% of emulsifier and the balance of water; the side chain of the silicon-containing polymer contains siloxane, and the basic structural unit of the siloxane is-Si (CH)3)2O-, the side chain content of the silicon-containing polymer is 5-50 wt%, the side chain molecular weight of the silicon-containing polymer is 200-50000, the carboxyl content of the silicon-containing polymer is 1-30 wt%, and the molecular weight of the silicon-containing polymer is 500-50000; the main chain of the silicon-containing polymer is formed by self polymerization of at least one unsaturated monomer of methacrylic acid, acrylic acid, maleic anhydride, maleic acid and itaconic acid or copolymerization of a plurality of unsaturated monomers; the silicon-containing polymerThe main chain also comprises one or more of ethyl acrylate, butyl acrylate, hexyl acrylate and octyl acrylate.
2. The silicon-containing retanning fatliquor according to claim 1, characterized in that the neutralizing agent is selected from one of sodium hydroxide solution, potassium hydroxide solution, ammonia water solution, ethanolamine solution, diethanolamine solution and triethanolamine solution, and the concentration of the neutralizing agent is 20-30 wt%.
3. The silicon-containing retanning fatliquor according to claim 1, characterized in that the emulsifier is selected from at least one of the isomeric tridecanol ethoxylates and fatty alcohol ethoxylates.
4. A silicon-containing retanning fatliquor according to any one of claims 1 to 3 wherein the silicon-containing retanning fatliquor has an effective solids content of 25% to 35% and a pH of 6.5 to 8.
5. The preparation method of the silicon-containing retanning fatliquor according to any one of claims 1 to 4, characterized in that the silicon-containing polymer, the neutralizing agent and the emulsifier are added into a reaction kettle, mixed and added with water at the stirring speed of 130-;
the weight percentages are as follows: 15-30 wt% of the silicon-containing polymer, 0-30 wt% of the neutralizing agent, 0-20 wt% of the emulsifier, and the balance of the water.
6. The method of claim 5, wherein the silicon-containing polymer is converted from a silicone oil.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534060A (en) * | 2011-12-21 | 2012-07-04 | 四川亭江新材料股份有限公司 | Method for preparing re-tanning and fatliquoring agent |
| CN102532382A (en) * | 2011-12-12 | 2012-07-04 | 东营黎宁化工有限公司 | Preparation method of polydiisobutylene-fatty monoamide maleate-acrylic acid leather retanning-fatting agent |
| CN103131804A (en) * | 2013-02-02 | 2013-06-05 | 四川德赛尔化工实业有限公司 | Amphiprotic amphiphilic leather retanning fatting agent and preparation method thereof |
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2017
- 2017-11-27 CN CN201711210173.6A patent/CN107937636B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102532382A (en) * | 2011-12-12 | 2012-07-04 | 东营黎宁化工有限公司 | Preparation method of polydiisobutylene-fatty monoamide maleate-acrylic acid leather retanning-fatting agent |
| CN102534060A (en) * | 2011-12-21 | 2012-07-04 | 四川亭江新材料股份有限公司 | Method for preparing re-tanning and fatliquoring agent |
| CN103131804A (en) * | 2013-02-02 | 2013-06-05 | 四川德赛尔化工实业有限公司 | Amphiprotic amphiphilic leather retanning fatting agent and preparation method thereof |
Non-Patent Citations (1)
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| 有机硅防水加脂剂的制备;宋密钊;《中国皮革》;20100131;第41-44页 * |
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