CN111944935B - Leather degreasing agent based on ionic liquid and preparation method thereof - Google Patents
Leather degreasing agent based on ionic liquid and preparation method thereof Download PDFInfo
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- CN111944935B CN111944935B CN202010611381.2A CN202010611381A CN111944935B CN 111944935 B CN111944935 B CN 111944935B CN 202010611381 A CN202010611381 A CN 202010611381A CN 111944935 B CN111944935 B CN 111944935B
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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
- C14C5/00—Degreasing leather
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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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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Abstract
The leather degreasing agent based on the ionic liquid comprises the following components in percentage by mass: 5-20% of ionic liquid, 5-17% of nonionic surfactant, 3-15% of anionic surfactant and 60-85% of water. The leather degreasing agent based on the ionic liquid provided by the invention utilizes the dispersing effect of the ionic liquid on collagen fibers and excellent solubility of the ionic liquid on grease, adopts the ionic liquid as a removing reagent of the grease of the raw leather, and combines the emulsifying, permeating and washing effects of nonionic and anionic surfactants to realize the high-efficiency degreasing of the raw leather. For different raw material skins, the degreasing rate is over 70 percent, the degreasing time can be shortened to be within 30 minutes, and the method has important practical application value. In addition, the invention also provides a preparation method of the leather degreasing agent based on the ionic liquid.
Description
Technical Field
The invention relates to the technical field of leather processing, in particular to a leather degreasing agent based on ionic liquid and a preparation method thereof.
Background
Leather products are favored because of their unique surface texture, excellent softness and durability. Leather is derived from various animal skins, the excellent properties of which derive from the tanning effect of tanning agents on raw leather collagen fibers and their subsequent finishing processing. However, the animal skin contains not only collagen fiber network, but also a great amount of grease and other lipoid substances on the surface and in glands, and the presence of the substances not only hinders the penetration of various chemical materials in the subsequent processing process, but also causes the defects of 'fat spots', 'metal soaps' and the like on the surface of the leather, thereby affecting the quality of the leather product. Therefore, degreasing the hide is an important process in leather production.
At present, degreasing methods of raw leather mainly comprise emulsification degreasing, alkaline degreasing, enzymatic degreasing, organic solvent degreasing and the like. However, these degreasing methods have certain drawbacks. The oil on the surface of the raw leather can be removed by the emulsification degreasing and the alkaline degreasing, but the internal oil removing effect is poor, and the subsequent further degreasing is needed, otherwise, the oil spots are generated on the finished product. The enzyme degreasing method can effectively remove the grease in the skin, but has high requirements on temperature and time control, enzyme inactivation is easily caused by improper temperature control, the production efficiency is influenced, and in addition, the collagen fiber network is easily damaged due to overlong enzyme treatment time. Although the degreasing effect of the organic solvent degreasing method is good, the organic solvent is volatile, and the environmental pollution is large. Therefore, the development of the novel environment-friendly and efficient degreasing agent has important significance for the sustainable development of the leather industry.
Disclosure of Invention
In view of the above, the invention provides a formula and a preparation method for applying ionic liquid to a leather degreasing agent, and aims to overcome the defects of the prior degreasing technology and improve the degreasing effect of raw leather.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the leather degreasing agent based on the ionic liquid comprises the following components in percentage by mass: 5-20% of ionic liquid, 5-17% of nonionic surfactant, 3-15% of anionic surfactant and 60-85% of water.
Further, the ionic liquid is: 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole hexafluorophosphate.
Further, the nonionic surfactant is: peregal O, octyl phenol polyoxyethylene ether OP-1, fatty alcohol polyoxyethylene ether AEO-9, tween-80 and span 80 or a mixture of a plurality of the materials.
Further, the anionic surfactant is: sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, N, N-oleoyl methyl sodium sulfonate, ethyl oleate sodium sulfonate and one or a mixture of more of oleamido sodium sulfonate.
A preparation method of a leather degreasing agent based on ionic liquid comprises the following steps:
s1 the method comprises the following steps: synthesis of ionic liquid:
s11: dissolving 1-methylimidazole in ethanol, dropwise adding 1-chlorobutane or 1-bromobutane into the ethanol solution of the 1-methylimidazole under the protection of inert gas, magnetically stirring for 2-10 hours at the temperature of 25-35 ℃, and cooling the reaction liquid to 0 ℃;
s12: extracting the reaction liquid by using ethyl acetate, drying and removing water to obtain ionic liquid 1-butyl-3-methylimidazolium chloride and 1-butyl-3-methylimidazolium bromide respectively;
s2: providing a nonionic surfactant, an anionic surfactant and water,
s3: and (2) mixing one or more of the ionic liquid prepared in the step (S1) with the nonionic surfactant, the anionic surfactant and water to obtain the leather degreasing agent based on the ionic liquid.
Further, the inert gas is one or two of nitrogen and helium.
Further, in step S1, a method for preparing an ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate is also included:
s13, dissolving the 1-butyl-3-methylimidazole chloride obtained in the step S12 in water, slowly adding hexafluorophosphoric acid while rapidly stirring at room temperature, stirring for 1-3 hours until the solution is layered, and pouring out an upper aqueous phase;
s14: washing the lower ionic liquid layer of the non-aqueous phase left in step S13 with water and a saturated aqueous sodium bicarbonate solution in this order;
s15: extracting with dichloromethane, and drying to obtain ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate.
Further, in step S1, a method for preparing an ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate is also included:
s23: dissolving the 1-butyl-3-methylimidazolium bromide obtained in the step S12 and ammonium tetrafluoroborate in methanol, magnetically stirring at 35-45 ℃ for 25-35 minutes, and stopping reaction;
s24: filtering to remove reaction by-product NH 4 Br；
S25: distilling to remove a portion of the methanol from the solvent;
s26: drying to completely remove residual methanol, and waiting until the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate is obtained.
Compared with the prior art, the leather degreasing agent based on the ionic liquid provided by the invention utilizes the advantages of the ionic liquid such as dispersion effect on collagen fibers and excellent solubility on grease, adopts the nonvolatile ionic liquid to replace an organic solvent as a degreasing agent for raw leather grease, combines the emulsification, permeation and washing effects of nonionic and anionic surfactants, can overcome the defects of the prior art, integrates the advantages of various existing degreasing methods, and can remarkably improve the degreasing effect and efficiency of the raw leather. The preparation method of the leather degreasing agent based on the ionic liquid has the advantages of easily available raw materials, low cost, simple preparation method and easy industrialization. In addition, the ionic liquid can be recycled after use, which is beneficial to protecting the environment and saving the cost.
Detailed Description
Specific examples of the present invention will be described in further detail below. It should be understood that the description herein of embodiments of the invention is not intended to limit the scope of the invention.
The leather degreasing agent based on the ionic liquid is composed of the ionic liquid, a nonionic surfactant, an anionic surfactant and water. The ionic liquid, also called ionic liquid, refers to a liquid composed entirely of anions and cations, such as KCI at high temperature, KOH in a liquid state, and in this case, they are ionic liquids. Substances that are liquid at or near room temperature and are composed of ions are also referred to as ionic liquids or room temperature ionic liquids. In the ionic compound, the acting force between the anions and cations is coulomb force, the magnitude of which is related to the charge quantity and radius of the anions and cations, and the larger the ionic radius is, the smaller the acting force between the anions and the cations is, and the lower the melting point of the ionic compound is. Some ionic compounds have bulky anions and cations and loose structures, resulting in low forces between them, such that the melting point is close to room temperature, thereby forming ionic liquids. In this example, the ionic liquid may be 1-butyl-3-methylimidazolium chloride (abbreviation: [ Bmim ]][Cl]) 1-butyl-3-methylimidazolium bromide (abbreviation: [ Bmim ]][Br]) 1-butyl-3-methylImidazole tetrafluoroborate (abbreviation: [ Bmim ]][BF 4 ]) 1-butyl-3-methylimidazolium hexafluorophosphate (abbreviation: [ Bmim ]][PF 6 ]One or a mixture of several of them. The ionic liquid is a prior art, and the formation principle, characteristics and the like thereof are not described in detail herein. In the leather degreasing agent, the mass percent of the ionic liquid is 5-20%, preferably, the mass percent of the ionic liquid is 8-15%, and more preferably, the weight percent of the ionic liquid is 10%. The nonionic surfactant is a surfactant which contains an ether group which is not dissociated in an aqueous solution or takes polyalcohol as a main hydrophilic group in a molecule, and the surface activity of the nonionic surfactant is represented by neutral molecules. The nonionic surfactant has high surface activity, good solubilization, washing, antistatic, calcium soap dispersion and other performances, small irritation, and excellent wetting and washing functions. Nonionic surfactants can be classified into polyoxyethylene type, polyhydric alcohol type, alkanolamide type, polyether type, amine oxide type, and the like according to the structure of the hydrophilic group. In this embodiment, the nonionic surfactant may be one or a mixture of peregal O, octylphenol polyoxyethylene ether OP-1, fatty alcohol polyoxyethylene ether AEO-9, tween-80 and span 80. The mass percent of the nonionic surfactant is 5-17%, preferably, the mass percent of the nonionic surfactant is 8-13%, and more preferably: the mass percentage content is 11 percent. The anionic surfactant is divided into the following components according to the structure of a hydrophilic group: sulfonates and sulfate salts are currently the major class of anionic surfactants. The various functions of surfactants are mainly manifested in changing the surface, liquid-liquid interface and liquid-solid interface properties of liquids. In this embodiment, the anionic surfactant may be one or more of sodium dodecyl benzene sulfonate (LAS), sodium Dodecyl Sulfate (SDS), sodium N, N-oleoyl methyl sulfonate (pancreatic plus drift T), sodium ethyl oleate sulfonate (pancreatic plus drift a), and sodium oleoyl amino acid (Lei Mibang a). The mass percentage content of the anionic surfactant is 3% -15%. Preferably, the content of the anionic surfactant is 5-12% by mass. Furthermore, the utility modelPreferably, the content thereof is 8% by mass. The water is preferably purified water, more preferably distilled water, to reduce impurities. The water content is 60-85 wt%, preferably 65-80 wt%, and more preferably 71 wt%.
The invention also provides a preparation method of the leather degreasing agent based on the ionic liquid, which comprises the following steps:
s1: synthesis of ionic liquid:
s11: dissolving 1-methylimidazole in ethanol, and reacting 1-chlorobutane or 1-
Dropping bromobutane into the ethanol solution of 1-methylimidazole, magnetically stirring at 25-35 deg.C for 2-10%
H, cooling the reaction solution to 0 ℃;
s12: extracting the reaction solution by using ethyl acetate, drying and dehydrating to respectively obtain ionic liquids
1-butyl-3-methylimidazolium chloride ([ Bmim ] [ Cl ]) and 1-butyl-3-methylimidazolium bromide ([ Bmim ] [ Br ]);
s2: providing a nonionic surfactant, an anionic surfactant and water,
s3: and (2) mixing one or more of the ionic liquid prepared in the step (S1) with the nonionic surfactant, the anionic surfactant and water to obtain the leather degreasing agent based on the ionic liquid.
In step S11, the inert gas may be one or both of nitrogen and helium. Nitrogen is preferred.
When 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim) is selected][BF 4 ]) When the 1-butyl-3-methylimidazolium tetrafluoroborate is used as an ionic liquid or is included in the ionic liquid, the synthesis of the ionic liquid further comprises the following steps:
s13, dissolving the 1-butyl-3-methylimidazolium chloride [ Bmim ] [ Cl ] obtained in the step S21 in water, slowly adding hexafluorophosphoric acid while rapidly stirring at room temperature, stirring for 1-3 hours until the solution is layered, and pouring out an upper aqueous phase;
s14: washing the lower ionic liquid layer with water and saturated aqueous sodium bicarbonate solution successively for the non-aqueous phase left in step S13;
s15: extracting with dichloromethane, and drying to obtain ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([ Bmim)][PF 6 ])。
When 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim) is selected][BF 4 ]) When the ionic liquid is used or the 1-butyl-3-methylimidazolium tetrafluoroborate is included in the ionic liquid, the synthesis of the ionic liquid further comprises the following steps:
s23: dissolving [ Bmim ] [ Br ] and ammonium tetrafluoroborate (NH 4BF 4) obtained in the step S12 in methanol, magnetically stirring at 35-45 ℃ for 25-35 minutes, and stopping reaction;
s24: filtering to remove reaction by-product NH 4 Br；
S25: distillation to remove a portion of the methanol;
s26: drying to remove methanol, and then waiting until the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim)][BF 4 ])。
When the ionic liquid comprises both 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium tetrafluoroborate, the synthesis of the ionic liquid further comprises the following steps:
s13: dissolving the [ Bmim ] [ Cl ] obtained in the step S21 in water, slowly adding hexafluorophosphoric acid while rapidly stirring at room temperature, stirring for 1-3 hours until the solution is layered, and pouring out an upper aqueous phase;
s14: washing the lower ionic liquid layer with water and saturated aqueous sodium bicarbonate solution successively on the aqueous phase left in step S13;
s15: extracting with dichloromethane, and drying to obtain ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([ Bmim)][PF 6 ])；
S16: dissolving [ Bmim ] [ Br ] and ammonium tetrafluoroborate (NH 4BF 4) obtained in the step S12 in methanol, magnetically stirring at 35-45 ℃ for 25-35 minutes, and stopping reaction;
s17: filtering to remove reaction by-product NH 4 Br；
S18: distilling to remove part of methanol;
s19: drying to remove methanol, and then waiting until ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim)][BF 4 ])。
Example 1
The preparation method comprises the following steps:
(1) Dissolving 1-methylimidazole in ethanol, dropwise adding 1-chlorobutane into the solution under the protection of nitrogen, wherein the molar ratio of 1-chlorobutane to 1-methylimidazole is 1.10, magnetically stirring the solution at 30 ℃ for 5 hours, cooling the reaction solution to 0 ℃, extracting the reaction solution by using ethyl acetate, and drying the reaction solution to obtain the ionic liquid 1-butyl-3-methylimidazole chloride ([ Bmim ] [ Cl ]), wherein the yield of 1-methylimidazole is 92%.
(2) The [ Bmim ] [ Cl ] is compounded with a nonionic surfactant, an anionic surfactant and water to prepare the degreasing agent, and the specific composition formula of the degreasing agent is as follows (the total amount is 100 parts): 1-butyl-3-methylimidazolium chloride ([ Bmim ] Cl): 5 parts of a mixture; 10 parts of peregal O; sodium dodecyl benzene sulfonate (LAS): 15 parts of (1); water: 75 parts of degreasing solution which is 12.5kg is prepared according to the proportion, the degreasing solution is added into a rotary drum to be stirred for 20min, the temperature is set to be 30 ℃, the rotating speed is 20 r/min, and all the components are uniformly mixed to obtain the leather degreasing agent.
Degreasing effect evaluation: 10kg of soaked cowhide is put into a rotary drum, the rotating speed is adjusted to be 8 r/min, the cowhide rotates for 60 min and is taken out of the drum, the fur of the cowhide is fresh and clean, the surface of the cowhide is clean, and the cowhide has no greasy feeling. The grease content of the raw material peel before and after degreasing is detected by sampling, the calculated degreasing rate is 72.3%, and the degreasing effect is higher than that of the prior degreasing technology. After the degreasing solution is recovered, the degreased leather is washed, the subsequent production is carried out according to the production process of the brown sofa leather without other degreasing operations, the final product has compact leather body and uniform grain surface color, and the quality of the finished product meets the requirement.
Example 2
(1) Dissolving 1-methylimidazole in ethanol, dropwise adding 1-bromobutane into the solution under the protection of helium, wherein the molar ratio of 1-bromobutane to 1-methylimidazole is 1.2, magnetically stirring the solution at 30 ℃ for 5 hours, cooling the reaction solution to 0 ℃, extracting the reaction solution by using ethyl acetate, and drying the reaction solution to obtain the ionic liquid 1-butyl-3-methylimidazole bromide ([ Bmim ] [ Br ]), wherein the yield of the ionic liquid relative to 1-methylimidazole is 95%.
(2) The [ Bmim ] [ Br ] is compounded with a nonionic surfactant, an anionic surfactant and water to prepare the degreasing agent, and the specific composition formula of the degreasing agent is as follows (the total amount is 100 parts): 10 parts of 1-butyl-3-methylimidazolium bromide ([ Bmim ] [ Br ]); octyl phenol polyoxyethylene ether OP-1:11 parts of sodium N, N-oleoylmethylsulfonate (pancreas plus float T): 8 parts of a mixture; water: 71 parts of degreasing agent which is 10kg is prepared according to the proportion, the degreasing agent is added into a rotary drum to be stirred for 20min, the temperature is set to be 45 ℃, the rotating speed is 20 r/min, and all the components are uniformly mixed to obtain the leather degreasing agent.
Degreasing effect evaluation: 10kg of soaked and fleshed sheep skin is put into a rotary drum, the rotating speed is adjusted to be 15 r/min and 25 min, the sheep skin is taken out of the drum, the surface of the sheep skin is not greasy, grease on the surface and in oil pits is removed, the grease content of the raw material skin before and after degreasing is detected by sampling, the degreasing rate is calculated to be 91.5%, and the degreasing rate is greatly superior to the degreasing effect of various existing degreasing agents. After the degreasing solution is recovered, the degreased leather is washed by water, the subsequent production is carried out according to the black clothing leather process, other degreasing operations are not added, the finished leather of the final product is soft, the color and luster of the leather are uniform, and the quality of the finished product meets the requirements of high-grade clothing leather.
Example 3
(1) Dissolving 1-methylimidazole in ethanol, dropwise adding 1-bromobutane into the solution under the protection of nitrogen, wherein the molar ratio of 1-bromobutane to 1-methylimidazole is 1.05, magnetically stirring the solution at 30 ℃ for 5 hours, cooling the reaction solution to 0 ℃, extracting the reaction solution by using ethyl acetate, and drying the reaction solution to obtain 1-butyl-3-methylimidazole bromide ([ Bmim ] [ Br ]), wherein the yield of the ionic liquid relative to 1-methylimidazole is 93 percent;
(2) Will [ Bmim ]][Br]And ammonium tetrafluoroborate (NH) 4 BF 4 ) Dissolved in methanol, NH 4 BF 4 And [ Bmim ]][Br]Is 1.3; magnetically stirring at 40 deg.C for 30 min, stopping reaction, filtering, distilling, drying to remove methanol, and waiting until ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborateSalt ([ Bmim)][BF 4 ]) The yield relative to 1-methylimidazole was 90%.
(3)[Bmim][BF 4 ]The degreasing agent is prepared by compounding a nonionic surfactant, an anionic surfactant and water, and the specific composition formula of the degreasing agent is as follows (the total amount is 100 parts): 1-butyl-3-methylimidazolium tetrafluoroborate ([ Bmim)]BF 4 ): 12 parts of (1); fatty alcohol polyoxyethylene ether AEO-9:5 parts of a mixture; sodium oleamidoate (Lei Mibang a): 15 parts, water: 68 parts of degreasing solution which is prepared into 20kg according to the proportion, adding the degreasing solution into a rotary drum, stirring for 20min, setting the temperature at 35 ℃ and the rotating speed at 20 revolutions per minute, and uniformly mixing the components to obtain the leather degreasing agent.
Degreasing effect evaluation: 10kg of soaked and degreased pigskin is put into a rotary drum, the rotating speed is adjusted to be 12 revolutions per minute, the pigskin is rotated for 50 minutes, the pigskin is taken out of the rotary drum, the pigskin surface is clean, the pigskin blank is not expanded, the degreasing fluid is milky white, the pighair can be pulled out forcibly, the oil pit on the pork surface is clear, the grease content of the raw material skin before and after degreasing is detected by sampling, the degreasing rate is calculated to be 75.3%, and the degreasing effect is superior to that of the existing various degreasing methods. After the degreasing solution is recovered, the degreased leather is washed by water, the subsequent production is carried out according to the production process of the lining leather of the pigskin brown shoes, other degreasing operations are not added, and the final product is uniform in color, soft and comfortable and good in product quality.
Example 4
(1) Dissolving 1-methylimidazole in ethanol, dropwise adding 1-chlorobutane into the solution under the protection of nitrogen, wherein the molar ratio of 1-chlorobutane to 1-methylimidazole is 1.15, magnetically stirring the solution at 30 ℃ for 5 hours, cooling the reaction solution to 0 ℃, extracting the reaction solution by using ethyl acetate, and drying the reaction solution to obtain the ionic liquid 1-butyl-3-methylimidazole chloride ([ Bmim ] [ Cl ]), wherein the yield of the ionic liquid relative to 1-methylimidazole is 93%.
(2) Will [ Bmim ]][Cl]Dissolving in water, slowly adding hexafluorophosphoric acid, hexafluorophosphoric acid and [ Bmim ] while stirring at normal temperature][Cl]Stirring for 2 hours until the solution is layered, pouring out the upper aqueous phase, washing the lower ionic liquid by water and saturated sodium bicarbonate aqueous solution in sequence, extracting by dichloromethane, and drying to obtain the ionic liquid 1-butylYl-3-methylimidazolium hexafluorophosphate ([ Bmim)][PF 6 ]) The yield relative to 1-methylimidazole was 92%.
(3)[Bmim][PF 6 ]The degreasing agent is prepared by compounding a nonionic surfactant, an anionic surfactant and water, and the specific composition formula of the degreasing agent is (the total amount is 100 parts) 1-butyl-3-methylimidazolium hexafluorophosphate ([ Bmim)][PF 6 ]): 15 parts of (1); tween 80;15 parts of (1); 10 parts of ethyl oleate sodium sulfonate (pancreas plus bleaching A); water: 60 parts; preparing 15kg of degreasing solution according to the proportion, adding the degreasing solution into a rotary drum, stirring for 20min, setting the temperature at 25 ℃ and the rotating speed at 20 revolutions per minute, and uniformly mixing the components to obtain the leather degreasing agent.
Degreasing effect evaluation: 10kg of goat skin after being soaked in water and degreased is taken and put into a rotary drum, the rotating speed is adjusted to be 10 r/min, the goat skin rotates for 30 min and is taken out of the drum, the subcutaneous tissue of the goat skin is removed completely, the skin surface is not damaged, the oil content of the raw material skin before and after degreasing is detected by sampling, and the degreasing rate is calculated to be 83.7%. The degreasing effect is superior to that of the prior art. After the degreasing solution is recovered, the degreased leather is washed by water, the subsequent production is carried out according to the production process of the blue goat leather upper leather, other degreasing operations are not added, and the final product has compact leather surface, uniform color, good leather strength and good elasticity.
Example 5
(1) Dissolving 1-methylimidazole in ethanol, dividing into two parts, respectively dropwise adding 1-chlorobutane and 1-bromobutane into the ethanol solution of the 1-methylimidazole under the protection of nitrogen gas, wherein the molar ratio of the 1-chlorobutane to the 1-bromobutane to the 1-methylimidazole is 1.1 and 1.17, respectively, magnetically stirring for 5 hours at 30 ℃, cooling the reaction liquid to 0 ℃, extracting by using ethyl acetate, and drying to obtain ionic liquids of 1-butyl-3-methylimidazole chloride ([ Bmim ] [ Cl ]) and brominated 1-butyl-3-methylimidazole bromide ([ Bmim ] [ Br ]), wherein the yield is 92 percent and 94 percent respectively.
(2) The degreasing agent is prepared by compounding ([ Bmim ] [ Cl ]), ([ Bmim ] [ Br ]), a nonionic surfactant, an anionic surfactant and water, and the specific composition formula comprises (the total amount is 100 parts): 1-butyl-3-methylimidazolium bromide ([ Bmim ] Br): 10 parts of (A); 1-butyl-3-methylimidazolium hexafluorochloride ([ Bmim ] [ Br ]): 10 parts of (A); peregal O:5 parts of a mixture; sodium ethyl oleate sulfonate (pancreas plus float a): 15 parts of (1); water: 60 parts of degreasing solution which is prepared into 25kg according to the proportion is added into a rotary drum to be stirred for 20min, the temperature is set to be 40 ℃, the rotating speed is 20 r/min, and all the components are mixed evenly.
Degreasing effect evaluation: 10kg of soaked cowhide is put into a rotary drum, the rotating speed is adjusted to be 15 r/min, the cowhide rotates for 40 min, the cowhide is taken out of the drum, a leather blank is not damaged or expanded, degreasing liquid is milky, the surface of the leather is not greasy, the grease content of the raw material leather before and after degreasing is detected by sampling, the calculated degreasing rate is 75.3%, and the degreasing effect is better. After the degreasing solution is recovered, the degreased leather is washed by water, the subsequent production is carried out according to the black head layer shoe upper leather process, other degreasing operations are not added, and the final product leather has smooth grain surface, uniform color and no oil spots.
Compared with the prior art, the leather degreasing agent based on the ionic liquid provided by the invention utilizes the advantages of the ionic liquid such as dispersion effect on collagen fibers and excellent solubility on grease, adopts non-volatile ionic liquid to replace an organic solvent as a degreasing agent of raw leather grease, combines the emulsification, permeation and washing effects of nonionic and anionic surfactants, can overcome the defects of the prior art, integrates the advantages of various existing degreasing methods, and can remarkably improve the degreasing effect and efficiency of raw leather. The preparation method of the leather degreasing agent based on the ionic liquid has the advantages of easily available raw materials, low cost, simple preparation method and easy industrialization. In addition, the ionic liquid can be recycled after use, which is beneficial to protecting the environment and saving the cost.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the scope of the present invention, and any modifications, equivalents or improvements that are within the spirit of the present invention are intended to be covered by the following claims.
Claims (5)
1. The leather degreasing agent based on the ionic liquid is characterized in that: the leather degreasing agent based on the ionic liquid is composed of the ionic liquid, a nonionic surfactant, an anionic surfactant and water, and the leather degreasing agent comprises the following components in percentage by mass: 5% -20% of ionic liquid, 5% -17% of nonionic surfactant, 3% -15% of anionic surfactant and 60% -85% of water, wherein the ionic liquid is: 1-butyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole bromide, 1-butyl-3-methylimidazole tetrafluoroborate and 1-butyl-3-methylimidazole hexafluorophosphate, wherein the nonionic surfactant is one or a mixture of more of the following components: peregal O, octyl phenol polyoxyethylene ether OP-1, fatty alcohol polyoxyethylene ether AEO-9, tween-80, one or more mixtures of span 80, the anionic surfactant is: sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, N, N-oleoyl methyl sodium sulfonate, ethyl oleate sodium sulfonate and one or a mixture of more of oleamido sodium sulfonate.
2. A method for preparing the ionic liquid-based leather degreaser of claim 1, comprising the steps of:
s1: synthesis of ionic liquid:
s11: dissolving 1-methylimidazole in ethanol, dropwise adding 1-chlorobutane or 1-bromobutane into the ethanol solution of the 1-methylimidazole under the protection of inert gas, magnetically stirring for 2-10 hours at the temperature of 25-35 ℃, and cooling the reaction liquid to 0 ℃;
s12: extracting the reaction liquid by using ethyl acetate, drying and removing water to obtain ionic liquid 1-butyl-3-methylimidazolium chloride and 1-butyl-3-methylimidazolium bromide respectively;
s2: providing a nonionic surfactant, an anionic surfactant and water;
s3: and (2) mixing one or more of the ionic liquid prepared in the step (S1) with the nonionic surfactant, the anionic surfactant and water to obtain the leather degreasing agent based on the ionic liquid.
3. The method for preparing a leather degreasing agent based on ionic liquid according to claim 2, characterized in that: the inert gas is one or two of nitrogen and helium.
4. The process for the preparation of ionic liquid-based leather degreasers according to claim 2, characterized in that: in step S1, a method for preparing an ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate is also included:
s13: dissolving the 1-butyl-3-methylimidazole chloride obtained in the step S12 in water, slowly adding hexafluorophosphoric acid while rapidly stirring at room temperature, stirring for 1-3 hours until the solution is layered, and pouring out an upper aqueous phase;
s14: washing the non-aqueous phase remaining in step S13 with water and a saturated aqueous sodium bicarbonate solution in this order;
s15: extracting with dichloromethane, and drying to obtain ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate.
5. The process for the preparation of ionic liquid-based leather degreasers according to claim 2, characterized in that: in step S1, a process for preparing an ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate is also included:
s23: dissolving the 1-butyl-3-methylimidazolium bromide obtained in the step S12 and ammonium tetrafluoroborate in methanol, magnetically stirring at 35-45 ℃ for 25-35 minutes, and stopping reaction;
s24: filtering to remove a reaction by-product NH4Br;
s25: distilling to remove a portion of the methanol from the solvent;
s26: drying to completely remove residual methanol to obtain the ionic liquid 1-butyl-3-methylimidazole tetrafluoroborate.
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