Collagen-phosphate salt hyperbranched amphoteric fatliquoring agent and preparation method

Abstract

The application discloses a collagen-phosphate salt hyperbranched amphoteric fatting agent and a preparation method thereof, and particularly relates to the following steps: preparing a hyperbranched polymer containing multiple terminal hydroxyl groups, and preparing a hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups; dissolving collagen in water, adding the hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups to perform a water bath heating reaction, adjusting the pH of the solution, filtering and evaporating to obtain a collagen hyperbranched amphoteric polymer; adding the collagen hyperbranched amphoteric polymer and diaphosphorus pentoxide to perform a reaction, adding water to perform a hydrolysis reaction, adjusting the pH, filtering and evaporating, dissolving the obtained crude product in chloroform, washing, filtering, removing chloroform under reduced pressure, and drying, and the amphoteric fatting agent can be used in a wide pH range, the penetration and absorption of the fatting agent can be controlled by adjusting the pH, and the amphoteric fatting agent has excellent antibacterial property, antistatic property, softness and fullness and other special properties.

Description

Technical Field

[0001] This invention belongs to the field of leather tanning technology, specifically relating to a collagen-phosphate salt hyperbranched amphoteric fatliquoring agent, and also to a method for preparing the collagen-phosphate salt hyperbranched amphoteric fatliquoring agent. Background Technology

[0002] For the leather industry, chromium-containing wastewater has always been a major problem plaguing enterprises, factories, and the entire industry. Many leather industry veterans have dedicated themselves to research and development to find the most suitable environmentally friendly tanning method for leather, and the emergence of chromium-free tanning has greatly alleviated this problem. Fatliquoring agents are an indispensable component, mainly used in the wet finishing stage of leather processing. Due to its unique tanning method, chromium-free tanning easily creates a negatively charged surface, which conflicts with the anionic nature of the wet finishing materials in traditional chromium tanning systems. This results in poor binding between the agent and the leather, leading to poor absorption.

[0003] Collagen is an amphoteric substance containing both amino and carboxyl groups, making it ideal as a raw material for amphoteric wet finishing materials. Phosphate ester-containing fatliquoring agents have strong resistance to acids, alkalis, and salts, providing permanent fatliquoring effects, and exhibiting good lubricity, softness, fullness, and filling properties. Collagen-phosphate ester hyperbranched polymers are synthesized by phosphorylating unmodified hydroxyl groups in hyperbranched polymers containing multiple epoxy groups and terminal hydroxyl groups, and then crosslinking with collagen to form hyperbranched polymers. This results in collagen-phosphate ester hyperbranched amphoteric fatliquoring agents with diversity and surface activity. Furthermore, hyperbranched polymers possess a highly branched three-dimensional structure and good biocompatibility. Summary of the Invention

[0004] The purpose of this invention is to provide a collagen-phosphate salt hyperbranched amphoteric fatliquoring agent, which can control the penetration and absorption of the fatliquoring agent by adjusting the pH, and has excellent antibacterial and antistatic properties.

[0005] Another object of the present invention is to provide a method for preparing a collagen-phosphate salt hyperbranched amphoteric fatliquoring agent.

[0006] The technical solution adopted in this invention is a collagen-phosphate ester hyperbranched amphoteric lipotropic agent, with the following general structural formula:

[0007]

[0008] Where n = 1 to 8, and M is diethanolamine or triethanolamine;

[0009]

[0010] Another technical solution adopted in this invention is a method for preparing a collagen-phosphate ester hyperbranched amphoteric lipotropic agent, which is specifically implemented according to the following steps:

[0011] Step 1: Prepare a hyperbranched polymer containing multiple terminal hydroxyl groups;

[0012] Step 2: Prepare a hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups;

[0013] Step 3: Dissolve 1-15 parts of collagen in 10-30 parts of water, add 1-30 parts of hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups, carry out water bath heating reaction, after completion, adjust the pH of the solution, filter, and rotary evaporate to obtain hyperbranched amphoteric collagen polymer.

[0014] Step 4: Add the hyperbranched amphoteric polymer of collagen and phosphorus pentoxide to the reactor for reaction, add water to carry out hydrolysis reaction, adjust pH, filter, rotary evaporate, dissolve the crude product in chloroform, wash, filter, remove chloroform under reduced pressure, dry, and obtain collagen-phosphate ester salt hyperbranched amphoteric polymer fatliquoring agent.

[0015] The invention is further characterized in that,

[0016] In step 1, specifically: ethanolamine and methyl acrylate are added to a reactor for reaction, followed by the addition of pentaerythritol and sodium hydroxide as an alkaline catalyst. The reaction is carried out under reflux, cooled, washed, filtered under reduced pressure, and then rotary evaporated to produce a hyperbranched polymer containing multiple terminal hydroxyl groups. The molar ratio of ethanolamine, methyl acrylate, and pentaerythritol is 1:1–3:2–4. The reaction temperature is 25–35°C, the reaction time is 2–5 h, and the reflux reaction temperature is 90–110°C for 8–10 h.

[0017] In step 2, specifically: the hyperbranched polymer containing multiple terminal hydroxyl groups obtained in step 1, epichlorohydrin, and copper chloride catalyst are placed in a reactor for reaction. During the reaction, dilute hydrochloric acid is added to control the pH between 5.0 and 7.0, the reaction temperature is 20 to 40°C, the reaction time is 3 to 6 hours, the mixture is filtered, subjected to reduced pressure, washed 2 to 3 times, and rotary evaporated to obtain a hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups. The molar ratio of the hyperbranched polymer containing multiple terminal hydroxyl groups to epichlorohydrin is 1:1 to 3.

[0018] In step 3, the relative molecular mass of collagen is 1000–3000; the reaction temperature is 30–50℃; the reaction time is 6–8h; and the pH of the solution is adjusted to 5.0–8.0 using NaHCO3.

[0019] In step 4, the reaction temperature is 30–50℃, the reaction time is 10–12 h, the hydrolysis reaction temperature is 20–40℃, the hydrolysis reaction time is 2–3 h, and the washing is performed 2–3 times.

[0020] In step 4, the amount of water added is 4-6% of the total mass of hyperbranched amphoteric collagen polymer and phosphorus pentoxide.

[0021] In step 4, a weak base is added to adjust the pH of the solution to 5.0-7.0. The weak base is diethanolamine or triethanolamine.

[0022] The beneficial effects of this invention are as follows: In the method of this invention, collagen is phosphorylated with a hyperbranched polymer containing epoxy groups and terminal hydroxyl groups to obtain a collagen-phosphate ester hyperbranched amphoteric fatliquoring agent. The terminal epoxy group hyperbranched polymer has multiple reaction sites, enabling it to undergo multi-point binding reactions with collagen and leather fibers. Furthermore, the material is non-toxic, biodegradable, and conforms to the principles of green chemistry. The terminal hydroxyl group hyperbranched polymer contains multiple hydroxyl groups, which can react with phosphorylation reagents, ultimately resulting in a product containing multiple hydrophilic and lipophilic groups. These groups bind with active groups on collagen fibers, giving the leather a softer, fuller, and more elastic feel, while simultaneously increasing the leather yield. Simultaneously, this amphoteric fatliquoring agent can be used within a wide pH range, and the penetration and absorption of the fatliquoring agent can be controlled by adjusting the pH. In addition, it also possesses excellent antibacterial, antistatic, and softening / fullness properties. Detailed Implementation

[0023] The present invention will now be described in detail with reference to specific embodiments.

[0024] The collagen-phosphate ester hyperbranched amphoteric lipotropic agent of the present invention has the following general structural formula:

[0025]

[0026] Where n = 1 to 8, and M is diethanolamine or triethanolamine;

[0027]

[0028] The present invention relates to a method for preparing a collagen-phosphate ester hyperbranched amphoteric lipotropic agent, which involves phosphorylating unmodified hydroxyl groups in a hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups, and simultaneously binding it with collagen to synthesize a collagen-phosphate ester hyperbranched amphoteric polymer lipotropic agent.

[0029] This invention introduces epoxy groups to crosslink with collagen and modifies the terminal hydroxyl groups to phosphate ester groups, thus preparing a hyperbranched amphoteric fatliquoring agent of collagen-phosphate ester salt with certain surfactant properties. It exhibits excellent emulsifying, biodegradable, and biocompatible properties, is environmentally friendly, and can be applied in the leather fatliquoring process to promote oil penetration and impart special properties to leather such as antibacterial, antistatic, dispersible, and soft / smooth properties. The specific implementation steps are as follows:

[0030] Step 1, preparing a hyperbranched polymer containing multiple terminal hydroxyl groups, specifically:

[0031] Ethanolamine and methyl acrylate are added to a reactor for reaction at a temperature of 25–35°C for 2–5 hours. Pentaerythritol is then added along with sodium hydroxide as an alkaline catalyst, and the mixture is subjected to reflux at a temperature of 90–110°C for 8–10 hours. After cooling, washing, vacuum filtration, and rotary evaporation, a hyperbranched polymer containing multiple terminal hydroxyl groups is obtained.

[0032] The molar ratio of ethanolamine, methyl acrylate, and pentaerythritol is 1:1-3:2-4;

[0033] The specific reaction equation is as follows:

[0034]

[0035] Step 2, preparing a hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups, specifically:

[0036] The hyperbranched polymer containing multiple terminal hydroxyl groups obtained in step 1, epichlorohydrin, and copper chloride catalyst are placed in a reactor for reaction. During the reaction, dilute hydrochloric acid can be added to control the pH between 5.0 and 7.0. The reaction temperature is 20 to 40°C, and the reaction time is 3 to 6 hours. The mixture is then filtered, subjected to reduced pressure, washed 2 to 3 times, and rotary evaporated to obtain a hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups.

[0037] The molar ratio of the hyperbranched polymer containing multiple terminal hydroxyl groups to epichlorohydrin is 1:1–3; the specific reaction equation is as follows:

[0038]

[0039] Step 3, preparing hyperbranched amphoteric collagen polymers; specifically:

[0040] Dissolve 1-15 parts of collagen in 10-30 parts of water, add 1-30 parts of hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups, and carry out a water bath heating reaction at 30-50℃ for 6-8 hours. After the reaction is completed, add NaHCO3 to adjust the pH of the solution to 5.0-8.0, filter, and rotary evaporate to obtain hyperbranched amphoteric collagen polymer.

[0041] The relative molecular mass of collagen is 1000–3000;

[0042] The specific reaction equation is as follows:

[0043]

[0044] Step 4: Prepare a collagen-phosphate ester hyperbranched amphoteric polymer liposome; specifically:

[0045] Hyperbranched amphoteric collagen polymer and phosphoric acid reagent phosphorus pentoxide (P2O5) were added to a reactor for reaction at 30–50 °C for 10–12 h. After the reaction was completed, water was added for hydrolysis at 20–40 °C for 2–3 h to hydrolyze the phosphoric acid into phosphate monoesters and diesters. A weak base was added to adjust the pH to 5.0–7.0. The mixture was then filtered and rotary evaporated to obtain a crude product. The crude product was dissolved in chloroform, washed 2–3 times, filtered, and the solvent chloroform was removed under reduced pressure. The product was then dried to obtain a collagen-phosphate ester salt hyperbranched amphoteric polymer fatliquoring agent.

[0046] The amount of water added is 4-6% of the total mass of hyperbranched amphoteric collagen polymer and phosphorylation reagent;

[0047] The weak base is diethanolamine or triethanolamine, and the amount of weak base added is 20-40% of the total mass of hyperbranched amphoteric collagen polymer, phosphorylation reagent and water.

[0048] The specific reaction equation is as follows:

[0049]

[0050] The terminal epoxy hyperbranched polymer of the present invention has multiple reaction sites, enabling it to bind to collagen and skin fibers at multiple points. Furthermore, the material is non-toxic, biodegradable, and conforms to the principles of green chemistry. The terminal hydroxyl hyperbranched polymer contains multiple hydroxyl groups that can react with phosphorylation reagents, resulting in an amphoteric fatliquoring agent containing multiple hydrophilic and lipophilic groups. This amphoteric fatliquoring agent can be used over a wide pH range, and its penetration and absorption can be controlled by adjusting the pH.

[0051] Example 1:

[0052] (1) Add ethanolamine and methyl acrylate to the reactor at a molar ratio of 1:1, control the reaction temperature at 25°C, and the reaction time for 2 hours. Then add pentaerythritol at a molar ratio of 2, and add a catalyst at the same time. Heat the reactor and control the temperature at 90°C to ensure uniform mixing. Heat the reactor under reflux for 8 hours, cool, wash, filter under reduced pressure, and rotary evaporate to obtain a hyperbranched polymer containing multiple terminal hydroxyl groups.

[0053] (2) Place the hyperbranched polymer containing multiple terminal hydroxyl groups in the reactor, add epichlorohydrin at a molar ratio of 1:1, add a catalyst, control the pH to 5.0, react for 3 hours, filter, reduce pressure, wash 3 times, and rotary evaporate to obtain the hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups.

[0054] (3) Dissolve 1 part of collagen in 10 parts of water, add hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups, heat in a water bath at 30°C for 6 hours, add NaHCO3 to adjust the pH to 5.0, filter and rotary evaporate to obtain hyperbranched amphoteric collagen polymer.

[0055] (4) The collagen hyperbranched amphoteric polymer and phosphorylation reagent P2O5 prepared in (3) above were added to the reactor in a molar ratio of 1:1. The reaction temperature was 30℃ and the reaction was carried out for 10 hours. After the reaction was completed, water was added to carry out hydrolysis reaction. The reaction temperature was controlled at 20℃ and the reaction was carried out for 2 hours to hydrolyze the phosphoric acid into phosphate monoester and diester. Weak base was added to neutralize the mixture and the pH was adjusted to about 5.0. The mixture was filtered and rotary evaporated to obtain crude product. The crude product was dissolved in chloroform, washed 3 times, filtered and the solvent chloroform was removed under reduced pressure, and dried to obtain collagen-phosphate salt hyperbranched amphoteric polymer fatliquoring agent.

[0056] Example 2

[0057] (1) Add ethanolamine and methyl acrylate to the reactor at a molar ratio of 1:2, control the reaction temperature at 30°C, and the reaction time at 3 hours. Then add pentaerythritol at a molar ratio of 3, and add a catalyst at the same time. Heat the reactor and control the temperature at 100°C to ensure that the mixture is uniform. Heat the reactor under reflux for 9 hours, cool, wash, filter under reduced pressure, and rotary evaporate to obtain a hyperbranched polymer containing multiple terminal hydroxyl groups.

[0058] (2) The hyperbranched polymer containing multiple terminal hydroxyl groups in (1) is placed in a reactor, epichlorohydrin is added at a molar ratio of 1:2, a catalyst is added, the pH is controlled to 6.0, the reaction is carried out for 4 hours, filtered, reduced pressure, washed 3 times, and rotary evaporated to obtain the hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups.

[0059] (3) Take 8 parts of collagen and dissolve them in 20 parts of water. Add a hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups. Heat in a water bath at 40°C for 7 hours. Add NaHCO3 to adjust the pH to 7.0. Filter and rotary evaporate to obtain hyperbranched amphoteric collagen polymer.

[0060] (4) The collagen hyperbranched amphoteric polymer and phosphorylation reagent P2O5 prepared in (3) above were added to the reactor at a molar ratio of 1:2. The reaction temperature was 40℃ and the reaction was carried out for 11 hours. After the reaction was completed, water was added to carry out hydrolysis reaction. The reaction temperature was controlled at 30℃ and the reaction was carried out for 3 hours to hydrolyze the phosphoric acid into phosphate monoester and diester. Weak base was added to neutralize the mixture and the pH was adjusted to about 6.0. The mixture was filtered and rotary evaporated to obtain crude product. The crude product was dissolved in chloroform, washed 3 times, filtered and the solvent chloroform was removed under reduced pressure, and dried to obtain collagen-phosphate salt hyperbranched amphoteric polymer fatliquoring agent.

[0061] Example 3

[0062] (1) Add ethanolamine and methyl acrylate to the reactor at a molar ratio of 1:3, control the reaction temperature at 35°C, and the reaction time at 5 hours. Then add pentaerythritol at a molar ratio of 4, and add a catalyst at the same time. Heat the reactor and control the temperature at 110°C to ensure uniform mixing. Heat under reflux for 10 hours, cool, wash, filter under reduced pressure, and rotary evaporate to obtain a hyperbranched polymer containing multiple terminal hydroxyl groups.

[0063] (2) Place the hyperbranched polymer containing multiple terminal hydroxyl groups in the reactor, add epichlorohydrin at a molar ratio of 1:4, add a catalyst, control the pH to 7.0, react for 6 hours, filter, reduce pressure, wash 3 times, and rotary evaporate to obtain the hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups.

[0064] (3) Take 15 parts of collagen and dissolve them in 30 parts of water. Add a hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups. Heat in a water bath at 50°C for 8 hours. Add NaHCO3 to adjust the pH to 8.0. Filter and rotary evaporate to obtain hyperbranched amphoteric collagen polymer.

[0065] (4) The collagen hyperbranched amphoteric polymer and phosphorylation reagent P2O5 prepared in (3) above were added to the reactor at a molar ratio of 1:3. The reaction temperature was 50℃ and the reaction was carried out for 12 hours. After the reaction was completed, water was added to carry out hydrolysis reaction. The reaction temperature was controlled at 40℃ and the reaction was carried out for 3 hours to hydrolyze the phosphoric acid into phosphate monoester and diester. Weak base was added to neutralize the mixture and the pH was adjusted to about 7.0. The mixture was filtered and rotary evaporated to obtain crude product. The crude product was dissolved in chloroform, washed 3 times, filtered and the solvent chloroform was removed under reduced pressure, and dried to obtain collagen-phosphate salt hyperbranched amphoteric polymer fatliquoring agent.

[0066] The performance of the amphoteric fatliquoring agent of the present invention was tested, and the experimental results are shown in Table 1 below. The fatliquoring agent of the present invention can improve the softness, thickening rate, fullness, elasticity and mechanical properties of the raw leather.

[0067] Table 1 Performance of Fat Additives

[0068] sample Test fatliquoring agent Collagen-phosphate ester hyperbranched amphoteric lipoprotein ester Shrinkage temperature Ts 45℃ 68℃ Thickness increase 32％ 75％ Tensile strength 12MPa 16MPa

[0069] This invention prepares a collagen-phosphate ester hyperbranched amphoteric fatliquoring agent by crosslinking and phosphorylation of collagen with a hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups. The terminal epoxy group hyperbranched polymer has multiple reaction sites, which can react with collagen and skin fibers at multiple points. It has strong resistance to acids, alkalis and salts, and has a permanent fatliquoring effect. At the same time, it increases the number of hydrophilic and hydrophobic groups, and has good lubricity, softness and fullness, and filling properties. It is biodegradable and meets the environmental protection requirements of clean production and the production concept of green and safe products.

Claims

1. A method for preparing a collagen-phosphate ester hyperbranched amphoteric lipotropic agent, characterized in that, The specific steps are as follows: Step 1: Prepare a hyperbranched polymer containing multiple terminal hydroxyl groups; specifically: Ethanolamine and methyl acrylate were added to a reactor and reacted at a temperature of 25-35°C for 2-5 hours. Pentaerythritol was then added along with sodium hydroxide as an alkaline catalyst, and the mixture was subjected to reflux at a temperature of 90-110°C for 8-10 hours. After cooling, washing, vacuum filtration, and rotary evaporation, a hyperbranched polymer containing multiple terminal hydroxyl groups was obtained. The molar ratio of ethanolamine, methyl acrylate, and pentaerythritol was 1:1-3:2-4. Step 2: Prepare a hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups; Specifically: The hyperbranched polymer containing multiple terminal hydroxyl groups obtained in step 1, epichlorohydrin, and copper chloride catalyst were placed in a reactor for reaction. During the reaction, dilute hydrochloric acid was added to control the pH between 5.0 and 7.

0. The reaction temperature was 20-40℃, and the reaction time was 3-6 hours. The mixture was filtered, subjected to reduced pressure, washed 2-3 times, and then rotary evaporated to obtain a hyperbranched polymer containing multiple terminal epoxy groups and terminal hydroxyl groups. The molar ratio of the hyperbranched polymer containing multiple terminal hydroxyl groups to epichlorohydrin was 1:1-3. Step 3: Dissolve 1-15 parts of collagen in 10-30 parts of water, add 1-30 parts of hyperbranched polymer containing multiple epoxy groups and terminal hydroxyl groups, and carry out a water bath heating reaction at a temperature of 30-50℃ for 6-8 hours. After the reaction is completed, adjust the pH of the solution to 5.0-8.0 using NaHCO3, filter, and rotary evaporate to obtain hyperbranched amphoteric collagen polymer. Step 4: Add hyperbranched amphoteric collagen polymer and phosphorus pentoxide to the reactor for reaction. Add water for hydrolysis. Add a weak base to adjust the pH of the solution to 5.0-7.

0. The weak base is diethanolamine or triethanolamine. Filter and rotary evaporate. Dissolve the crude product in chloroform, wash, filter, remove chloroform under reduced pressure, and dry to obtain collagen-phosphate salt hyperbranched amphoteric polymer fatliquoring agent.

2. The preparation method of the collagen-phosphate ester hyperbranched amphoteric lipotropic agent as described in claim 1, characterized in that, In step 3, the relative molecular mass of collagen is 1000~3000.

3. The preparation method of the collagen-phosphate ester hyperbranched amphoteric lipotropic agent as described in claim 1, characterized in that, In step 4, the reaction temperature is 30~50℃, the reaction time is 10~12h, the hydrolysis reaction temperature is 20~40℃, the hydrolysis reaction time is 2~3h, and the washing is performed 2~3 times.

4. The preparation method of the collagen-phosphate ester hyperbranched amphoteric lipotropic agent as described in claim 1, characterized in that, In step 4, the amount of water added is 4-6% of the total mass of hyperbranched amphoteric collagen polymer and phosphorus pentoxide.

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