CN115404289A - Reactive fat-liquoring agent and preparation method thereof - Google Patents
Reactive fat-liquoring agent and preparation method thereof Download PDFInfo
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- CN115404289A CN115404289A CN202210963034.5A CN202210963034A CN115404289A CN 115404289 A CN115404289 A CN 115404289A CN 202210963034 A CN202210963034 A CN 202210963034A CN 115404289 A CN115404289 A CN 115404289A
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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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention belongs to the field of leather-making chemical industry, and discloses a reactive fat liquor and a preparation method thereof. According to the invention, epoxidized soybean oil is taken as a raw material, firstly, the ring opening is carried out on the epoxidized soybean oil through a hydroxyl compound, then, the ring opening is reacted with epoxy chloropropane to prepare chlorine-terminated triglyceride, and finally, the chlorine-terminated triglyceride is compounded with an emulsifier to obtain the reactive fat liquoring agent based on the epoxidized soybean oil. During the fatting process, chlorine atoms in the fatting agent can react with amino groups on the collagen fibers so as to be combined with the collagen fibers. Compared with the electrovalence combination mode of the common anionic fatting agent and the collagen fiber, the combination mode is firmer, can endow the fatting agent with better combination property and migration resistance, and is suitable for chrome tanning and chrome-free tanning systems with weaker positive electricity.
Description
Technical Field
The invention relates to the field of tanning chemical industry, in particular to a reactive fat-liquoring agent and a preparation method thereof.
Background
The greasing is one of the important steps in the leather production process, and can wrap grease on the surfaces of collagen fibers through physical and chemical actions to form an oil film with a lubricating effect among the collagen fibers, so that the softness, fullness and elasticity of the leather are improved, and the tensile strength and the tearing strength of the leather are improved.
The fat liquor is one of core materials used in the fat liquor process, and mainly comprises a fat component and an emulsifier component. The grease components commonly used in the current greasing agent are mainly natural animal and vegetable grease such as fish oil, lard oil, modified rape oil, castor oil and the like, and the grease has good greasing performance and can endow leather with good oil wettability and fullness after being compounded with an emulsifier. However, the natural animal and vegetable oil and fat often contains a large amount of unsaturated double bonds, and the double bonds are easily oxidized by air, so that the phenomena of yellowing, peculiar smell and the like are generated in the use process of finished leather, and the quality of the finished leather is influenced. In addition, the number of polar groups in the molecular structure of the traditional natural animal and vegetable oil is small, the oil can be combined with collagen fibers only through physical adsorption and hydrogen bond action in the greasing process, and the oil component is easy to migrate and is not resistant to water washing in the finished leather storage process. Under the condition, the method for preparing the novel fatting agent with yellowing resistance, strong binding capacity with collagen fibers and good storage stability by modifying natural animal and vegetable oil becomes the development direction of the fatting agent.
Epoxidized soybean oil is a product obtained by epoxidizing soybean oil and has the characteristics of wide source and environmental friendliness. Literature (research on gold residuum, perovskite oxide, znO quantum dot and modified epoxy soybean oil nano composite fatting agent [ D)]Shaanxi university of science and technology, 2020.) esterification of epoxidized soybean oil and maleic anhydride to synthesize soybean oil maleic acid monoester, and then sulfonic acid groups are introduced through sulfonation reaction to prepare the Gemini type modified epoxidized soybean oil fatting agent. The fatting agent can improve chrome tanningThe leather is soft and plump, and can be endowed with good yellowing resistance. It is worth noting that sulfonic acid groups are introduced in the preparation process of the fatting agent, and the sulfonic acid groups have strong negative charges. In the process of chrome tanning fatting, sulfonic acid group in the fatting agent can be matched with-NH in crust leather 2 、Cr 3+ Etc. are combined with each other by electrostatic interaction, and thus exhibit better migration resistance. However, for organic tanned leather, because the crust leather has weak positive electricity, the currently common anionic fatting agent has weak binding ability with collagen fibers and limited fatting performance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides the anti-yellowing reactive fat-liquoring agent prepared by using the epoxy soybean oil.
In order to achieve the purpose, the invention adopts a scheme that:
the reactive fat-liquoring agent comprises 15-45 parts of chlorotriglyceride and 2-6 parts of emulsifier by weight;
wherein the structural formula of the chlorine-terminated triglyceride is as follows:
in the formula, R 1 Is composed of
、
、
Any of the above.
Preferably, the chlorine-terminated triglyceride is obtained by ring-opening epoxidized soybean oil by a hydroxyl-containing compound and then reacting with epichlorohydrin.
Preferably, the hydroxyl-containing compound includes, but is not limited to, lactic acid, ethanolamine, diethanolamine.
Preferably, the weight ratio of the epoxidized soybean oil to the hydroxyl compound to the epoxy chloropropane is (2 to 4): 1 to 2.5.
Preferably, the epoxidized soybean oil has an epoxy value greater than 6.
Preferably, the emulsifier is selected from tween 80 and/or span 80.
The invention adopts another technical scheme that:
a method of preparing a reactive fatliquor, comprising the steps of:
mixing the epoxidized soybean oil and a hydroxyl compound at room temperature, adding a first catalyst, heating to 80 to 130 ℃, and reacting for 4 to 8 hours to obtain an epoxidized soybean oil ring-opening product;
mixing the ring-opening product of the epoxidized soybean oil with epichlorohydrin at room temperature, adding a second catalyst, heating to 70-90 ℃, and reacting for 6-10 h to obtain a chlorine-terminated triglyceride; and
mixing the chlorine-terminated triglyceride and an emulsifier, and stirring at 70 to 90 ℃ for 1 to 2 hours.
Preferably, the first catalyst is selected from any one or more of tetrabutylammonium bromide, triphenylphosphine and zinc chloride;
the second catalyst is selected from triphenylphosphine and/or boron trifluoride diethyl etherate.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, epoxidized soybean oil is used as a raw material, firstly, a hydroxyl compound is used for carrying out ring opening on the epoxidized soybean oil, then the epoxidized soybean oil reacts with epichlorohydrin to prepare chlorine-terminated triglyceride, and finally, the chlorine-terminated triglyceride is compounded with an emulsifier to obtain the reactive fat-liquoring agent based on the epoxidized soybean oil. During the fatting process, chlorine atoms in the fatting agent can react with amino groups on the collagen fibers so as to be combined with the collagen fibers. Compared with the electrovalence combination mode of the common anionic fatting agent and the collagen fibers, the combination mode is firmer, can endow the fatting agent with better combination property and migration resistance, and is suitable for chrome tanning and chrome-free tanning systems with weaker positive electricity.
According to the invention, epoxidized soybean oil with high saturation is used as a raw material, and unsaturated double bonds are not introduced in the reaction process, so that the product has good photo-thermal stability, and the fatted leather is resistant to yellowing and free of peculiar smell.
The raw materials of the fatting agent are green and environment-friendly, the product is suitable for chrome tanned leather and chrome-free tanned leather, has the advantages of good fatting effect, high absorptivity and yellowing resistance, and provides a new way for preparing the reactive fatting agent.
Drawings
FIG. 1 is an infrared spectrum of a product b obtained by ring-opening epoxidized soybean oil a and lactic acid and epoxidized soybean oil c in example 1 of the present invention;
FIG. 2 is the NMR carbon spectra of epoxidized soybean oil a and lactic acid ring-opened product b and chlorine-terminated triglyceride c in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. 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 first embodiment of the invention provides a reactive fatliquor, which comprises 15-45 parts of chlorine-terminated triglyceride and 2-6 parts of emulsifier by weight;
wherein the structural formula of the chlorine-terminated triglyceride is as follows:
in the formula, R 1 Is composed of
、
、
Any of the above.
The combination mode is firmer than the electrovalence combination mode of the anion fatting agent and the collagen fiber in the prior art, the fatting agent can be endowed with better combination property and migration resistance, and the method can be simultaneously suitable for chrome tanning and a chrome-free tanning system with weaker positive electricity.
The chlorine-terminated triglyceride is obtained by ring opening of epoxidized soybean oil by a hydroxyl-containing compound and then reacting with epichlorohydrin.
Wherein the structural formula of the epoxidized soybean oil is shown in the specification
Wherein R and R' are long carbon chains, and the number of carbon atoms is 5 to 10.
The structural formula of a ring-opening product of epoxidized soybean oil subjected to ring opening by a hydroxyl-containing compound is shown in the specification
In the formula, R 2 Is composed of
、
、
Any of the above.
For the choice of hydroxyl-containing compound, the structure should be such that: the epoxy soybean oil ring-opening agent contains hydroxyl and also contains an active functional group which has higher reactivity with an epoxy group than the hydroxyl, so that the epoxy soybean oil ring-opening agent can react with epoxy chloropropane to introduce chlorine atoms. In some preferred embodiments, the hydroxyl containing compound includes, but is not limited to, lactic acid, ethanolamine, diethanolamine.
The raw materials are preferably used in such an amount that the above reaction can sufficiently occur, and in some preferred embodiments, the weight ratio of the epoxidized soybean oil, the hydroxyl compound and the epichlorohydrin is (2 to 4): 1 (1 to 2.5).
In order to make the ring-opening reaction more sufficient and facilitate the introduction of more active chlorine atoms in the subsequent reaction with epichlorohydrin, epoxidized soybean oil with an epoxy value greater than 6 is preferred in the embodiment of the invention.
The emulsifier is a common emulsifier in the field, and the preferred embodiment of the invention is tween 80 and/or span 80.
In a second embodiment, the present invention provides a method for preparing a reactive fatliquor, the method comprising the steps of: mixing the epoxidized soybean oil and a hydroxyl compound at room temperature, adding a first catalyst, heating to 80 to 130 ℃, and reacting for 4 to 8 hours to obtain an epoxidized soybean oil ring-opening product;
mixing the ring-opening product of the epoxidized soybean oil with epichlorohydrin at room temperature, adding a second catalyst, heating to 70 to 90 ℃, and reacting for 6 to 10 hours to obtain a chlorine-terminated triglyceride; and
mixing the chlorotriglyceride and the emulsifier, and stirring for 1 to 2 hours at the temperature of 70 to 90 ℃.
The first catalyst is selected from one or more of tetrabutylammonium bromide, triphenylphosphine and zinc chloride;
the second catalyst is selected from triphenylphosphine and/or boron trifluoride diethyl etherate.
In order to better understand the technical scheme provided by the invention, the preparation method and the application performance are respectively illustrated by a plurality of specific examples.
The yellowing resistance, physical and mechanical properties, softness, thickness and absorption of the crust leather after retanning, mentioned in the following application examples and comparative application examples, were measured by a yellowing resistance test chamber (GT-7035-NUAB, high-speed iron testing instruments, inc.), a tensile tester (GT-AI-7000S, high-speed iron testing instruments, inc.), a leather softness tester (GT-303, high-speed iron testing instruments, inc.), a thickness tester (GT-313, high-speed iron testing instruments, inc.) and a total organic carbon analyzer (Liqui TOC, elementar, germany), respectively.
The following application examples and application pairsThe organic solvent resistance mentioned for the ratios is determined by the following method: cutting crust leather into 2mm multiplied by 2mm particles, weighing leather sample particles (mass is recorded as m) 1 ) And wrapped with filter paper. Extracting the particles wrapped by the filter paper by using dichloromethane as a solvent, taking out after 4 hours, drying at 105 ℃ to constant weight, and taking out leather sample particles (the mass is recorded as m) after constant weight 2 ). Meanwhile, weighing unextracted blank leather-like particles (the mass is recorded as m) 3 ) Drying at 105 ℃ to constant weight (mass is recorded as m) 4 ). The methylene chloride extract content omega in the leather was calculated according to the following formula. The lower the dichloromethane extract content, the better the resistance of the leather to organic solvent extraction.
Example 1
Preparing a reactive fatting agent:
mixing 112.5 g of lactic acid, 2.25 g of tetrabutylammonium bromide and 4.5 g of triphenylphosphine, adding the mixture into a three-neck flask, stirring at normal temperature for 10 min, adding 300 g of epoxidized soybean oil, heating to 80 ℃, and stirring for reacting for 8 h to obtain an epoxidized soybean oil ring-opening product. Mixing the product with 7 g of triphenylphosphine in a three-neck flask at normal temperature, adding 210 g of epoxy chloropropane, heating to 70 ℃, and stirring for reaction for 10 hours. And taking out the product, and stirring and mixing the product with 56 g of Tween 80 at 70 ℃ for 2 h to obtain the epoxidized soybean oil-based reactive fat liquor.
In this example, the infrared spectra of epoxidized soybean oil a, product b obtained by ring-opening epoxidized soybean oil with lactic acid, and chlorotriglyceride c are shown in fig. 1, and the nuclear magnetic resonance carbon spectrum is shown in fig. 2.
Map a in FIG. 1 is at 824 cm -1 、1242 cm -1 The peak is a characteristic peak of epoxy group in the molecular structure of the epoxidized soybean oil, and the peak completely disappears in the graph b, which proves that the reaction of the lactic acid and the epoxidized soybean oil is successful, and the carboxyl group of the lactic acid completely opens the epoxy group. In addition, 3442 cm in atlas b -1 The broad association peak is the characteristic absorption peak of hydroxyl, and the peak is generated due to the reaction of lactic acid and epoxidized soybean oil to generate polyolThe compound also confirmed the occurrence of the epoxy ring-opening reaction. 668 cm in the spectrum c-terminal chlorotriglyceride -1 The peak is the C-Cl stretching vibration peak, and the appearance of the peak confirms the successful reaction of the epoxidized soybean oil polyalcohol product and the epichlorohydrin. Furthermore, 1132 cm in FIG. c -1 The absorption peak is from ether bond generated after the epoxy chloropropane is subjected to ring opening by hydroxyl, and strong evidence is provided for successful reaction of the lactic acid ring opening product and the epoxy chloropropane.
In fig. 2, the absorption peak at 56 ppm of the spectrum a comes from the carbon of the epoxy group in the epoxidized soybean oil, and the peak completely disappears in the spectrum b, which proves that the lactic acid is completely reacted with the epoxidized soybean oil and the epoxy group is completely consumed. Meanwhile, the absorption peaks of 62ppm and 66 ppm in the graph b are characteristic absorption peaks of carbon connected with hydroxyl, and successful ring opening of lactic acid is also confirmed to generate the polyol compound. And the absorption peak of 46-48 ppm in the spectrum c is the absorption peak of carbon connected with chlorine atoms in the generated chlorine-terminated triglyceride after the reaction of the epoxidized soybean oil polyalcohol and the epichlorohydrin, and the successful introduction of the chlorine atoms in the fat liquor is proved.
Example 2
Preparing a reactive fatting agent:
mixing 55 g of lactic acid, 1.25 g of tetrabutylammonium bromide and 3.5 g of triphenylphosphine, adding the mixture into a three-neck flask, stirring at normal temperature for 10 min, adding 200 g of epoxidized soybean oil, heating to 80 ℃, and stirring for reacting for 8 h to obtain an epoxidized soybean oil ring-opening product. And mixing the product with 3.5 g of boron trifluoride diethyl etherate in a three-neck flask at normal temperature, adding 130 g of epoxy chloropropane, heating to 70 ℃, stirring for reacting for 6 hours, taking out the product, and stirring and mixing with 20 g of span 80 at 80 ℃ for 1 hour to obtain the reactive fat liquoring agent based on the epoxidized soybean oil.
Example 3
Preparing a reactive fatting agent:
mixing 65 g of ethanolamine, 1.5 g of tetrabutylammonium bromide, 1.5 g of triphenylphosphine and 1.5 g of zinc chloride, adding the mixture into a three-neck flask, stirring for 10 min at normal temperature, adding 250 g of epoxidized soybean oil, heating to 80 ℃, and stirring for reacting for 6 h to obtain an epoxidized soybean oil ring-opening product. And mixing the product with 3.2 g of boron trifluoride diethyl etherate in a three-neck flask at normal temperature, adding 160 g of epoxy chloropropane, heating to 80 ℃, stirring for reacting for 8 hours, taking out the product, stirring and mixing with 43 g of Tween 80 at 70 ℃ for 2 hours, and obtaining the reaction type fatliquor based on epoxidized soybean oil.
Example 4
Preparing a reactive fatliquor:
100 g of diethanolamine, 2.5 g of zinc chloride and 4 g of triphenylphosphine are mixed, added into a three-neck flask, stirred at normal temperature for 10 min, then 300 g of epoxidized soybean oil is added, the temperature is raised to 120 ℃, and the mixture is stirred and reacted for 4 h, so that an epoxidized soybean oil ring-opening product is obtained. And mixing the product with 5 g of triphenylphosphine in a three-neck flask at normal temperature, adding 160 g of epoxy chloropropane, heating to 70 ℃, stirring for reacting for 8 hours, taking out the product, and stirring and mixing with 32 g of span 80 at 70 ℃ for 1 hour to obtain the reactive fatliquor based on the epoxidized soybean oil.
Example 5
Preparing a reactive fatliquor:
and (2) mixing 135 g of diethanolamine, 2 g of tetrabutylammonium bromide, 2 g of triphenylphosphine and 2 g of zinc chloride, adding the mixture into a three-neck flask, stirring at normal temperature for 10 min, adding 300 g of epoxidized soybean oil, heating to 100 ℃, and stirring for reacting for 4 h to obtain an epoxidized soybean oil ring-opening product. And mixing the product with 7.5 g of boron trifluoride diethyl etherate in a three-neck flask at normal temperature, adding 176 g of epoxy chloropropane, heating to 90 ℃, stirring for reaction for 4 hours, taking out the product, and stirring and mixing with 60 g of tween 80 at 70 ℃ for 2 hours to obtain the reactive fat-liquoring agent based on epoxidized soybean oil.
Application example 1
This application example fatliquoring of cow leather sofa leather with the reactive fatliquor prepared in example 1:
putting the uniformly shaved blue leather as the raw material of the cowhide sofa leather into a rotary drum, sequentially softening, washing and retanning according to the conventional process, then adding 8 percent of reactive fatting agent and 100 percent of water by weight of the uniformly shaved blue leather, rotating for 1 hour at the temperature of 50 ℃, adding acid for fixation for four times, adding 0.5 percent of formic acid each time and rotating for 15 min.
The cow leather blue wet skin treated by the process is fatliquored, the thickening rate is 21.15%, the softness is 8.84 mm, the tearing strength is 99.77N/mm, the absorptivity of a fatliquoring agent is 94.26%, the content of a dichloromethane extract is 4.98%, the yellowing resistance grade is 4, and the grain surface is flat, fine, full and soft.
Application example 2
This application example fatliquoring of sheepskin leather using the reactive fatliquor prepared in example 3:
putting the uniformly-cut sheep clothing leather raw material into a rotary drum, softening, washing and retanning the raw material according to a conventional process in sequence, adding 8% of reactive fatting agent and 100% of water by weight of the uniformly-cut blue leather, rotating the mixture for 1 h at the temperature of 50 ℃, adding acid for fixation for four times, adding 0.5% of formic acid each time, and rotating the mixture for 15 min.
The wet sheep skin blue leather treated by the process is fatliquored, the thickening rate is 18.97%, the softness is 8.91 mm, the tearing strength is 83.25N/mm, the absorptivity of a fatliquoring agent is 93.35%, the content of a dichloromethane extract is 5.23%, the yellowing resistance grade is 4, and the wet sheep skin blue leather is plump and soft and has excellent comprehensive performance.
Application example 3
This application example fatliquoring an aldehyde-tanned cowhide upper leather using the reactive fatliquor prepared in example 4:
putting the evenly shaved white leather of the aldehyde tanned cow leather upper leather raw material into a rotary drum, softening, washing and retanning sequentially according to the conventional process, adding 10 percent of reactive fatting agent and 150 percent of water according to the weight of the evenly shaved white leather after draining, rotating for 1 h at the temperature of 50 ℃, adding 0.4 percent of formic acid twice for fixation, and rotating for 15 min.
After the white and wet cowhide skin treated by the process is fatliquored, the thickening rate is 18.84%, the softness is 8.58 mm, the tearing strength is 104.22N/mm, the absorptivity of a fatliquoring agent is 95.78%, the content of a dichloromethane extract is 5.54%, the yellowing resistance grade is 3.5, the finished leather is full, and the physical and mechanical properties are excellent.
Application example 4
This application example fatliquoring a TWLZ tanned cow leather upper leather using the reactive fatliquor prepared in example 5:
putting the evenly shaved white leather of the TWLZ tanned cow leather upper leather raw material into a rotary drum, sequentially softening, washing and retanning according to a conventional process, adding 10% of reactive fatting agent and 150% of water according to the weight of the evenly shaved white leather after draining, rotating for 1 h at the temperature of 50 ℃, adding 0.4% of formic acid twice for fixation, and rotating for 15 min each time.
The thickening rate of the white wet leather of the cow leather treated by the process is 18.41 percent after greasing, the softness is 8.23 mm, the tearing strength is 106.57N/mm, the absorptivity of the greasing agent is 94.77 percent, the content of dichloromethane extract is 4.86 percent, the yellowing resistance grade is 3.5 grade, the finished leather is compact, and the physical and mechanical properties are excellent.
Comparative application example
This comparative example is a cow leather sofa leather fatliquored with a commercial rapeseed oil fatliquoring agent:
putting uniformly shaved blue leather of a cowhide sofa leather raw material into a rotary drum, softening, washing and retanning the uniformly shaved blue leather raw material according to a conventional process in sequence, adding 8 percent of reactive fat liquor according to the weight of the uniformly shaved blue leather, 100 percent of water, rotating the uniformly shaved blue leather raw material for 1 hour at the temperature of 50 ℃, adding acid for fixing for four times, adding 0.5 percent of formic acid every time, and rotating the uniformly shaved blue leather raw material for 15 minutes.
The softness, the absorptivity of the fatliquor, the physical and mechanical properties, the organic solvent extraction resistance and the yellowing resistance of finished leather tests obtained after the fatliquoring of the application example 1 and the application comparative example are compared, and the results are shown in the following table:
as can be seen from the table, the cowhide sofa leather fatted by the reactive fat-liquoring agent prepared by using the epoxy soybean oil is similar to the commercial fat-liquoring agent in softness, and the physical and mechanical properties and the fat-liquoring agent absorptivity are superior to the commercial fat-liquoring agent, which indicates that the epoxy soybean oil reactive fat-liquoring agent prepared by the method has better fat-liquoring property. Meanwhile, the content of the methylene chloride extract of the crust leather of the application example 1 is obviously lower than that of the crust leather of the application comparative example, and the yellowing resistance grade is higher than that of the application comparative example, which shows that the organic solvent extraction resistance and the yellowing resistance of the crust leather fatliquored by the fatliquoring agent prepared by the method are better than those of the crust leather fatliquored by the commercial fatliquoring agent.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The reactive fatting agent is characterized by comprising 15-45 parts of chlorotriglyceride and 2-6 parts of emulsifier by weight;
wherein the structural formula of the chlorine-terminated triglyceride is as follows:
in the formula, R 1 Is composed of
、
、
Any of the above.
2. Reactive fatliquor according to claim 1, characterised in that the chlorotriglyceride is obtained by ring opening of epoxidized soybean oil with a hydroxyl-containing compound and subsequent reaction with epichlorohydrin.
3. Reactive fatliquor according to claim 2, wherein the hydroxyl containing compound comprises but is not limited to lactic acid, ethanolamine, diethanolamine.
4. The reactive fatliquor according to claim 2, wherein the weight ratio of the epoxidized soybean oil to the hydroxyl compound to the epichlorohydrin is (2 to 4) to 1 to (1 to 2.5).
5. Reactive fatliquor according to claim 2, wherein the epoxidized soybean oil has an epoxy value of greater than 6.
6. Reactive fatliquor according to claim 1, characterised in that the emulsifier is selected from tween 80 and/or span 80.
7. Method for preparing a reactive fatliquor according to any one of claims 1 to 6, comprising the steps of:
mixing the epoxidized soybean oil and a hydroxyl compound at room temperature, adding a first catalyst, heating to 80 to 130 ℃, and reacting for 4 to 8 hours to obtain an epoxidized soybean oil ring-opening product;
mixing the ring-opening product of the epoxidized soybean oil with epichlorohydrin at room temperature, adding a second catalyst, heating to 70-90 ℃, and reacting for 6-10 h to obtain a chlorine-terminated triglyceride; and
mixing the chlorotriglyceride and the emulsifier, and stirring for 1 to 2 hours at the temperature of 70 to 90 ℃.
8. The method of claim 7, wherein the first catalyst is selected from any one or more of tetrabutylammonium bromide, triphenylphosphine, and zinc chloride;
the second catalyst is selected from triphenylphosphine and/or boron trifluoride diethyl etherate.
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