Intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent and preparation method thereof
By modifying the fatliquoring agent with sodium phytate-intercalated hydrotalcite and castor oil through phosphoric acid esterification, the problem of poor dispersibility and compatibility of flame retardant components was solved, and high-performance flame retardant leather with good softness and thermal stability was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHAANXI UNIV OF SCI & TECH
- Filing Date
- 2026-04-29
- Publication Date
- 2026-06-05
AI Technical Summary
The existing fatliquoring agents have poor dispersibility and compatibility of flame retardant components, resulting in low flame retardant efficiency and making it difficult to meet the application requirements of high-performance flame retardant leather.
Sodium phytate intercalated hydrotalcite and castor oil were used for phosphoric acid esterification modification. By controlling the interlayer structure, in-situ composite of intercalated hydrotalcite and phosphoric acid esterified castor oil was achieved, thereby improving its dispersion stability and compatibility.
This forms a structurally stable composite system that improves the flame retardancy and softness of leather, while reducing the risk of combustion and exhibiting good thermal stability and charring ability.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of leather chemicals technology, and relates to an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. This invention also relates to a method for preparing the above-mentioned intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. Background Technology
[0002] Fatliquoring is a crucial step in leather tanning. It involves introducing oil-based fatliquoring agents into the leather fiber structure, allowing them to distribute between collagen fibers and act as a lubricant, thereby improving the leather's softness, fullness, and elasticity. However, fatliquoring agents are primarily composed of oily substances. While imparting excellent softness to the leather, they can increase heat release during combustion or decrease heat resistance, leading to insufficient flame retardancy. In particular, they are prone to high heat release rates and weak charring ability during combustion, making it difficult to meet the application requirements of high-performance flame-retardant leather and, to some extent, affecting the leather's safety performance.
[0003] Castor oil, a widely available natural vegetable oil, boasts advantages such as low cost, non-toxicity, and renewability, making it widely used in leather fatliquoring to effectively improve the softness and feel of leather. However, in practical applications, fatliquoring agents with castor oil as the main component are prone to oil migration and accumulation on the leather surface under heating conditions, leading to increased flammability and thus limiting its application in fields requiring high flame retardancy.
[0004] Current research has attempted to introduce functional components to improve flame retardant performance. However, in practical applications, functional components often have a layered structure, which is prone to agglomeration and stacking in fatliquoring agents. The flame retardant components have poor dispersibility and compatibility, making it difficult to form a stable and uniform dispersion system, thus limiting the flame retardant performance. Summary of the Invention
[0005] The purpose of this invention is to provide a method for preparing a composite fatliquoring agent of intercalated hydrotalcite / phosphate-modified castor oil. This method involves using sodium phytate-intercalated hydrotalcite and phosphate-modified castor oil. The interlayer structure of layered double hydroxide (LDH) is regulated by sodium phytate intercalation, and in-situ composite formation is achieved during the phosphate esterification process of castor oil. This improves the dispersion stability of LDH in phosphate-modified castor oil and enhances the compatibility of the two components. This solves the problems of poor dispersion and compatibility of flame-retardant components and low flame-retardant efficiency in existing fatliquoring agents.
[0006] A second objective of this invention is to provide an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0007] A third objective of this invention is to provide the application of an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0008] The technical solution adopted in this invention is a method for preparing an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent, which is implemented according to the following steps: Step 1, Preparation of intercalated hydrotalcite (Phy-LDH); Step 1.1: Prepare the metal salt solution; Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution; Step 1.3, Preparation of Phy-LDH; Step 2: Prepare an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent; Step 2.1, prepare the reaction solution; Step 2.2: Add Phy-LDH to the reaction solution; Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0009] The invention is further characterized by: Step 1.1 specifically involves preparing a metal salt solution using magnesium nitrate (Mg(NO3)2·6H2O) and aluminum nitrate (Al(NO3)3·9H2O) as the metal salt sources. + / Al³ + The molar ratio is (1.5-3):1.
[0010] Step 1.2 specifically involves preparing a 0.5-1.5 mol / L sodium phytate aqueous solution and adding a metal salt solution to the sodium phytate aqueous solution under stirring conditions to obtain a mixed solution. Maintain the temperature at 78-84℃ while stirring.
[0011] Step 1.3 specifically involves: adjusting and maintaining the pH of the mixed solution at 9.8-10.2 using NaOH solution, setting the reaction temperature at 78-84℃, and allowing the reaction time to be 0.8-1.2 hours. After the reaction was completed, crystallization was continued for 11-13 hours, followed by centrifugation at 6000-8000 rpm, washing with deionized water 3-5 times, and drying to constant weight to obtain Phy-LDH.
[0012] Step 2.1 specifically involves mixing castor oil with TMP, adding NaOH catalyst, and obtaining a reaction solution.
[0013] The molar ratio of castor oil to trimethyl phosphate (TMP) is 1:(2.5-3.5), and the mass of NaOH catalyst is 0.3%-0.7% of the mass of castor oil.
[0014] Step 2.2 is as follows: Nitrogen gas is introduced into the container holding the reaction solution for 5 minutes to establish an oxygen-free environment. Phy-LDH is added during the heating stage or 0-1 hours after the start of the reaction. The temperature is raised to 118-122℃ under nitrogen protection and the reaction is carried out for 5.5-6.5 hours. The mass of Phy-LDH accounts for 6%-12% of the mass of the reaction solution. It is added in batches, in 2-4 batches, with the same amount added in each batch, and the amount added in each batch is 1.5%-3% of the mass of the reaction solution.
[0015] Step 2.3 specifically involves: after the reaction is completed, using rotary evaporation at 60-80℃ to remove the alcohol byproducts generated during the reaction, and cooling to room temperature to obtain the intercalated hydrotalcite / phosphate esterified modified castor oil composite fatliquoring agent.
[0016] The second technical solution adopted in this invention is an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent, which is obtained by the preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0017] The third technical solution adopted in this invention is the application of intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent, and the application of intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent in the preparation of leather with flame-retardant properties.
[0018] The beneficial effects of this invention are: (1) The present invention uses sodium phytate intercalated hydrotalcite to expand the interlayer spacing and weaken the interlayer electrostatic effect, reduce the tendency of lamellar aggregation, and improve the dispersion stability of LDH in castor oil; at the same time, the castor oil is modified by phosphoric acid esterification, and phosphorus-containing groups are introduced into its molecules, thereby improving its compatibility with hydrotalcite, so that the phosphoric acid esterified castor oil and sodium phytate intercalated hydrotalcite can be uniformly combined to form a structurally stable composite system.
[0019] (2) The intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent of the present invention has both softening and flame-retardant functions. Phosphate-modified castor oil improves the affinity and binding strength with collagen fibers, giving leather good softness and migration resistance; sodium phytate intercalated hydrotalcite works synergistically with organophosphorus components to improve the thermal stability and char-forming ability of the material, reduce the risk of combustion, and the system is green, low in toxicity and highly integrated in function. Detailed Implementation
[0020] The following detailed description is provided in conjunction with specific implementation methods.
[0021] The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent is carried out according to the following steps: Step 1: Prepare Phy-LDH.
[0022] Step 1.1, Prepare the metal salt solution Weigh out Mg(NO3)2·6H2O and Al(NO3)3·9H2O, and prepare a metal salt solution using Mg(NO3)2·6H2O and Al(NO3)3·9H2O as metal salt sources. + / Al³ + The molar ratio is (1.5-3):1.
[0023] Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution.
[0024] Prepare a 0.5-1.5 mol / L sodium phytate aqueous solution, and add a metal salt solution to the sodium phytate aqueous solution under stirring to obtain a mixed solution.
[0025] Maintain the temperature at 78-84℃ while stirring.
[0026] Step 1.3, prepare Phy-LDH.
[0027] The pH of the mixed solution was adjusted and maintained at 9.8-10.2 using NaOH solution, so that metal ions could be co-precipitated in the presence of phytate to form intercalated hydrotalcite precursors. The reaction temperature was 78-84℃ and the reaction time was 0.8-1.2h.
[0028] After the reaction was completed, crystallization was continued for 11-13 hours, followed by centrifugation at 6000-8000 rpm, washing with deionized water 3-5 times, and drying to constant weight to obtain Phy-LDH, which is intercalated hydrotalcite obtained by regulating the interlayer structure through sodium phytate intercalation.
[0029] Step 2: Prepare intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0030] Step 2.1, prepare the reaction solution.
[0031] Castor oil and TMP were added to a reactor at a molar ratio of 1:(2.5-3.5), and NaOH catalyst was added to obtain a reaction solution.
[0032] The amount of NaOH is 0.3%-0.7% of the weight of castor oil.
[0033] Step 2.2: Add Phy-LDH to the reaction solution.
[0034] Nitrogen gas is introduced into the container holding the reaction solution for 5 minutes to establish an anaerobic environment. Phy-LDH is added during the heating phase or 0-1 hours after the start of the reaction. The temperature is raised to 118-122℃ under nitrogen protection and the reaction is carried out for 5.5-6.5 hours. This allows Phy-LDH to disperse in the reaction solution and undergo in-situ complexation with the phosphoric acid esterified modified castor oil (PMCO) generated in situ.
[0035] Phy-LDH should be added in batches of 6%-12% of the reaction solution mass, in 2-4 batches, with each batch containing the same amount of 1.5%-3% of the reaction solution mass.
[0036] Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. After the reaction was completed, the alcohol byproducts generated during the reaction were removed by rotary evaporation at 60-80℃, and then cooled to room temperature to obtain the intercalated hydrotalcite / phosphate esterified modified castor oil composite fatliquoring agent.
[0037] An intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent was obtained using a preparation method for an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0038] Application of intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent in the preparation of leather with flame-retardant properties.
[0039] Example 1 The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent is carried out according to the following steps: Step 1: Prepare Phy-LDH.
[0040] Step 1.1, Prepare the metal salt solution Weigh out Mg(NO3)2·6H2O and Al(NO3)3·9H2O, and prepare a metal salt solution using Mg(NO3)2·6H2O and Al(NO3)3·9H2O as metal salt sources. + / Al³ + The molar ratio is 2:1.
[0041] Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution.
[0042] Prepare a 1 mol / L sodium phytate aqueous solution, and add a metal salt solution to the sodium phytate aqueous solution under stirring to obtain a mixed solution.
[0043] Maintain the temperature at 80℃ while stirring.
[0044] Step 1.3, prepare Phy-LDH.
[0045] The pH of the mixed solution was adjusted and maintained at 10 using NaOH solution, so that metal ions could be co-precipitated in the presence of phytate to form an intercalated hydrotalcite precursor. The reaction temperature was 80℃ and the reaction time was 1h.
[0046] After the reaction was completed, crystallization was continued for 12 hours, followed by centrifugation, washing with deionized water three times, and drying to constant weight to obtain Phy-LDH.
[0047] Step 2: Prepare intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0048] Step 2.1, prepare the reaction solution.
[0049] 46.67 g (0.05 mol) of castor oil and 1.01 g (0.15 mol) of TMP were added to a reactor, and 0.23 g of NaOH catalyst (0.5% of the mass of castor oil) was added to obtain a reaction solution.
[0050] Step 2.2: Add Phy-LDH to the reaction solution.
[0051] A nitrogen atmosphere was introduced into the container holding the reaction solution for 5 minutes to establish an anaerobic environment. Phy-LDH was added during the heating phase, and the mixture was heated to 120°C and reacted for 6 hours under nitrogen protection. This allowed the Phy-LDH to disperse in the reaction solution and recombine with the PMCO generated in situ.
[0052] Phy-LDH accounts for 6% of the mass of the reaction solution and is added in batches, in two batches, with each batch containing the same amount, and each batch containing 3% of the mass of the reaction solution.
[0053] Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. After the reaction was completed, the alcohol byproducts generated during the reaction were removed by rotary evaporation at 60°C, and then cooled to room temperature to obtain the intercalated hydrotalcite / phosphate esterified modified castor oil composite fatliquoring agent.
[0054] Example 2 The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent is carried out according to the following steps: Step 1: Prepare Phy-LDH.
[0055] Step 1.1, Prepare the metal salt solution Weigh out Mg(NO3)2·6H2O and Al(NO3)3·9H2O, and prepare a metal salt solution using Mg(NO3)2·6H2O and Al(NO3)3·9H2O as metal salt sources. + / Al³ + The molar ratio is 2:1.
[0056] Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution.
[0057] Prepare a 1 mol / L sodium phytate aqueous solution, and add a metal salt solution to the sodium phytate aqueous solution under stirring to obtain a mixed solution.
[0058] Maintain the temperature at 80℃ while stirring.
[0059] Step 1.3, prepare Phy-LDH.
[0060] The pH of the mixed solution was adjusted and maintained at 10 using NaOH solution, so that metal ions could be co-precipitated in the presence of phytate to form an intercalated hydrotalcite precursor. The reaction temperature was 80℃ and the reaction time was 1h.
[0061] After the reaction was completed, crystallization was continued for 12 hours, followed by centrifugation, washing with deionized water three times, and drying to constant weight to obtain Phy-LDH.
[0062] Step 2: Prepare intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0063] Step 2.1, prepare the reaction solution.
[0064] 46.67 g (0.05 mol) of castor oil and 1.01 g (0.15 mol) of TMP were added to a reactor, and 0.23 g of NaOH catalyst (0.5% of the mass of castor oil) was added to obtain a reaction solution.
[0065] Step 2.2: Add Phy-LDH to the reaction solution.
[0066] A nitrogen atmosphere was introduced into the container holding the reaction solution for 5 minutes to establish an anaerobic environment. Phy-LDH was added during the heating phase, and the mixture was heated to 120°C and reacted for 6 hours under nitrogen protection. This allowed the Phy-LDH to disperse in the reaction solution and recombine with the PMCO generated in situ.
[0067] Phy-LDH accounts for 8% of the mass of the reaction solution and is added in batches, divided into 4 batches. The amount added in each batch should be the same, and the amount added in each batch is 2% of the mass of the reaction solution.
[0068] Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. After the reaction was completed, the alcohol byproducts generated during the reaction were removed by rotary evaporation at 60°C, and then cooled to room temperature to obtain the intercalated hydrotalcite / phosphate esterified modified castor oil composite fatliquoring agent.
[0069] Example 3 The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent is carried out according to the following steps: Step 1: Prepare Phy-LDH.
[0070] Step 1.1, Prepare the metal salt solution Weigh out Mg(NO3)2·6H2O and Al(NO3)3·9H2O, and prepare a metal salt solution using Mg(NO3)2·6H2O and Al(NO3)3·9H2O as metal salt sources. + / Al³ + The molar ratio is 2:1.
[0071] Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution.
[0072] Prepare a 1 mol / L sodium phytate aqueous solution, and add a metal salt solution to the sodium phytate aqueous solution under stirring to obtain a mixed solution.
[0073] Maintain the temperature at 80℃ while stirring.
[0074] Step 1.3, prepare Phy-LDH.
[0075] The pH of the mixed solution was adjusted and maintained at 10 using NaOH solution, so that metal ions could be co-precipitated in the presence of phytate to form an intercalated hydrotalcite precursor. The reaction temperature was 80℃ and the reaction time was 1h.
[0076] After the reaction was completed, crystallization was continued for 12 hours, followed by centrifugation, washing with deionized water three times, and drying to constant weight to obtain Phy-LDH.
[0077] Step 2: Prepare intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0078] Step 2.1, prepare the reaction solution.
[0079] 46.67 g (0.05 mol) of castor oil and 1.01 g (0.15 mol) of TMP were added to a reactor, and 0.23 g of NaOH catalyst (0.5% of the mass of castor oil) was added to obtain a reaction solution.
[0080] Step 2.2: Add Phy-LDH to the reaction solution.
[0081] A nitrogen atmosphere was introduced into the container holding the reaction solution for 5 minutes to establish an anaerobic environment. Phy-LDH was added during the heating phase, and the mixture was heated to 120°C and reacted for 6 hours under nitrogen protection. This allowed the Phy-LDH to disperse in the reaction solution and recombine with the PMCO generated in situ.
[0082] Phy-LDH accounts for 12% of the mass of the reaction solution and is added in batches of 3 batches, with each batch containing the same amount of 4% of the mass of the reaction solution.
[0083] Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. After the reaction was completed, the alcohol byproducts generated during the reaction were removed by rotary evaporation at 60°C, and then cooled to room temperature to obtain the intercalated hydrotalcite / phosphate esterified modified castor oil composite fatliquoring agent.
[0084] Example 4 The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent is carried out according to the following steps: Step 1: Prepare Phy-LDH.
[0085] Step 1.1, Prepare the metal salt solution Weigh out Mg(NO3)2·6H2O and Al(NO3)3·9H2O, and prepare a metal salt solution using Mg(NO3)2·6H2O and Al(NO3)3·9H2O as metal salt sources. + / Al³ + The molar ratio is 3:1.
[0086] Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution.
[0087] Prepare a 1.5 mol / L sodium phytate aqueous solution, and add a metal salt solution to the sodium phytate aqueous solution under stirring to obtain a mixed solution.
[0088] Maintain the temperature at 84℃ while stirring.
[0089] Step 1.3, prepare Phy-LDH.
[0090] The pH of the mixed solution was adjusted and maintained at 10.2 using NaOH solution, so that metal ions could be co-precipitated in the presence of phytate to form an intercalated hydrotalcite precursor. The reaction temperature was 84℃ and the reaction time was 1.2h.
[0091] After the reaction was completed, crystallization was continued for 13 hours, followed by centrifugation at 8000 rpm, washing with deionized water 5 times, and drying to constant weight to obtain Phy-LDH.
[0092] Step 2: Prepare intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0093] Step 2.1, prepare the reaction solution.
[0094] Castor oil and TMP were added to a reactor at a molar ratio of 1:3.5, and NaOH catalyst was added to obtain a reaction solution.
[0095] The mass of NaOH is 0.7% of the mass of castor oil.
[0096] Step 2.2: Add Phy-LDH to the reaction solution.
[0097] Nitrogen gas was introduced into the container holding the reaction solution for 5 minutes to establish an anaerobic environment. Phy-LDH was added 1 hour after the start of the reaction. The temperature was raised to 122°C under nitrogen protection and the reaction was carried out for 6.5 hours. This allowed Phy-LDH to disperse in the reaction solution and undergo in-situ complexation with the phosphoric acid esterified castor oil (PMCO) generated in situ.
[0098] Phy-LDH accounts for 12% of the mass of the reaction solution and is added in batches, divided into 4 batches. The amount added in each batch should be the same, and the amount added in each batch is 3% of the mass of the reaction solution.
[0099] Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. After the reaction was completed, the alcohol byproducts generated during the reaction were removed by rotary evaporation at 80°C, and then cooled to room temperature to obtain the intercalated hydrotalcite / phosphorylated castor oil composite fatliquoring agent.
[0100] Example 5 The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent is carried out according to the following steps: Step 1: Prepare Phy-LDH.
[0101] Step 1.1, Prepare the metal salt solution Weigh out Mg(NO3)2·6H2O and Al(NO3)3·9H2O, and prepare a metal salt solution using Mg(NO3)2·6H2O and Al(NO3)3·9H2O as metal salt sources. + / Al³ + The molar ratio is 1.5:1.
[0102] Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution.
[0103] Prepare a 0.5-1.5 mol / L sodium phytate aqueous solution, and add a metal salt solution to the sodium phytate aqueous solution under stirring to obtain a mixed solution.
[0104] Maintain the temperature at 78°C while stirring.
[0105] Step 1.3, prepare Phy-LDH.
[0106] The pH of the mixed solution was adjusted and maintained at 9.8 using NaOH solution, so that metal ions could be co-precipitated in the presence of phytate to form an intercalated hydrotalcite precursor. The reaction temperature was 78℃ and the reaction time was 0.8h.
[0107] After the reaction was completed, crystallization was continued for 11 hours, followed by centrifugation at 6000 rpm, washing with deionized water three times, and drying to constant weight to obtain Phy-LDH.
[0108] Step 2: Prepare intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0109] Step 2.1, prepare the reaction solution.
[0110] Castor oil and TMP were added to a reactor at a molar ratio of 1:2.5, and NaOH catalyst was added to obtain a reaction solution.
[0111] The mass of NaOH is 0.3% of the mass of castor oil.
[0112] Step 2.2: Add Phy-LDH to the reaction solution.
[0113] Nitrogen gas was introduced into the container holding the reaction solution for 5 minutes to establish an anaerobic environment. Phy-LDH was added during the heating phase, and the temperature was raised to 118°C under nitrogen protection and reacted for 5.5 hours. This allowed Phy-LDH to disperse in the reaction solution and undergo in-situ complexation with the in-situ generated phosphoric acid esterified modified castor oil (PMCO).
[0114] Phy-LDH should be added in batches, with each batch consisting of 6% of the reaction solution mass. The amount added in each batch should be the same, and the amount added in each batch should be 3% of the reaction solution mass.
[0115] Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent. After the reaction was completed, the alcohol byproducts generated during the reaction were removed by rotary evaporation at 60°C, and then cooled to room temperature to obtain the intercalated hydrotalcite / phosphate esterified modified castor oil composite fatliquoring agent.
[0116] Example 6 An intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent was obtained using a preparation method for an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
[0117] Comparative Example 1 46.67 g (0.05 mol) of castor oil, 21.01 g (0.15 mol) of trimethyl phosphate (TMP), and 0.14 g (0.3% of the castor oil mass) of sodium hydroxide were added to a 1000 mL three-necked flask. A reflux condenser, a nitrogen inlet, and a mechanical stirrer were installed. Nitrogen gas was introduced for 5 min to establish an anaerobic environment. The temperature was raised to 120 °C and the reaction was carried out under stirring for 6 h. After the reaction was completed, the alcohol byproducts generated during the reaction were removed by rotary evaporation at 60 °C. The mixture was then cooled to room temperature to obtain the modified castor oil fatliquoring agent.
[0118] The intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent prepared in this invention uses renewable castor oil as the organic phase source and low-toxicity, environmentally friendly sodium phytate as the intercalated inorganic functional phase. No additional emulsifier is added during the preparation process. The process route is simple, the conditions are controllable, and it is suitable for scale-up. It has good green sustainability and cost controllability, and provides an effective technical idea and method for the construction and application of environmentally friendly functionalized composite fatliquoring agent system.
[0119] Intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent and phosphate-modified castor oil fatliquoring agent were used for leather fatliquoring treatment to prepare fatliquored leather, and the limiting oxygen index and softness of the obtained leather were measured. The results of Example 3 and Comparative Example 1 showed that the leather treated with the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent had a limiting oxygen index of 33.5%, significantly higher than that of the leather treated with the phosphate-modified castor oil fatliquoring agent (29.2%); simultaneously, its softness was 5.3 mm, basically consistent with the 5.2 mm of the control leather. This indicates that while maintaining good softness, the composite fatliquoring agent of this application can significantly improve the flame retardant properties of the leather, resulting in superior overall performance.
[0120] Table 1 Comparison of results between Example 3 and Comparative Example 1
Claims
1. A method for preparing an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent, characterized in that, The specific steps are as follows: Step 1, prepare Phy-LDH; Step 1.1: Prepare the metal salt solution; Step 1.2: Prepare an aqueous solution of sodium phytate and mix it with a metal salt solution to obtain a mixed solution; Step 1.3, Preparation of Phy-LDH; Step 2: Prepare an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent; Step 2.1, prepare the reaction solution; Step 2.2: Add Phy-LDH to the reaction solution; Step 2.3: Prepare the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent.
2. The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent according to claim 1, characterized in that, Step 1.1 specifically involves: weighing Mg(NO3)2·6H2O and Al(NO3)3·9H2O, and preparing a metal salt solution using Mg(NO3)2·6H2O and Al(NO3)3·9H2O as metal salt sources. + / Al³ + The molar ratio is (1.5-3):
1.
3. The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent according to claim 1, characterized in that, Step 1.2 specifically involves: preparing a 0.5-1.5 mol / L sodium phytate aqueous solution, and adding a metal salt solution to the sodium phytate aqueous solution under stirring conditions to obtain a mixed solution; Maintain the temperature at 78-84℃ while stirring.
4. The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent according to claim 1, characterized in that, Step 1.3 specifically involves: adjusting and maintaining the pH of the mixed solution to 9.8-10.2 using NaOH solution, setting the reaction temperature to 78-84℃, and the reaction time to 0.8-1.2h. After the reaction was completed, crystallization was continued for 11-13 hours, followed by centrifugation at 6000-8000 rpm, washing with deionized water 3-5 times, and drying to constant weight to obtain Phy-LDH.
5. The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent according to claim 1, characterized in that, Step 2.1 specifically involves mixing castor oil with TMP, adding NaOH catalyst, and obtaining a reaction solution.
6. The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent according to claim 5, characterized in that, The molar ratio of castor oil to TMP is 1:(2.5-3.5), and the mass of the NaOH catalyst is 0.3%-0.7% of the mass of castor oil.
7. The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent according to claim 1, characterized in that, Step 2.2 specifically involves: purging nitrogen gas into the container holding the reaction solution for 5 minutes to establish an oxygen-free environment; adding Phy-LDH during the heating phase or 0-1 hours after the start of the reaction; and heating to 118-122°C under nitrogen protection and reacting for 5.5-6.5 hours. The Phy-LDH mass accounts for 6%-12% of the reaction solution mass and is added in batches of 2-4 batches, with each batch having the same amount, and each batch having an amount of 1.5%-3% of the reaction solution mass.
8. The preparation method of the intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent according to claim 1, characterized in that, Step 2.3 specifically involves: after the reaction is completed, using rotary evaporation at 60-80℃ to remove the alcohol byproducts generated during the reaction, and cooling to room temperature to obtain the intercalated hydrotalcite / phosphate esterified modified castor oil composite fatliquoring agent.
9. An intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent, characterized in that, It is obtained by the preparation method of the intercalated hydrotalcite / phosphorylation modified castor oil composite fatliquoring agent according to any one of claims 1-8.
10. The application of an intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent, characterized in that, Application of intercalated hydrotalcite / phosphate-modified castor oil composite fatliquoring agent in the preparation of leather with flame-retardant properties.