Preparation method of jatropha oil-based waterborne polyurethane emulsion

Abstract

The invention discloses a preparation method of jatropha curcas oil-based waterborne polyurethane emulsion, and relates to a preparation method of a high polymer material polyurethane emulsion, the method is a synthesis method of amino silicon oil (KH550) modified bio-based polyurethane used in the textile field, jatropha curcas oil is used as a raw material, and functional molecular design is adopted to prepare the jatropha curcas oil-based waterborne polyurethane emulsion. KH550 is introduced by virtue of a catalyst-free green chemical process to synthesize controllable jatropha curcas oil-based polyol, and the controllable jatropha curcas oil-based polyol is further polymerized with isophorone diisocyanate (IPDI) through chain structure design to prepare a jatropha curcas oil-based waterborne polyurethane coating dispersion which is subsequently applied to the surface of a fabric. The preparation method aims at preparing the high-performance textile coating and enhancing the hydrophobic and antifouling properties of the fabric. The work not only has important significance on design and application of a sustainable bio-based waterborne polyurethane textile finishing agent in the textile industry, but also widens the application field of non-grain bio-based materials.

Description

Technical Field

[0001] This invention relates to a method for preparing a polyurethane emulsion, specifically a method for preparing a jatropha oil-based waterborne polyurethane emulsion. Background Technology

[0002] High-performance bio-based waterborne polyurethane (BWPU), as a substitute for petroleum-based polyurethane materials, can be widely used in light industry, chemical industry, electronics, textiles, medical, construction, automotive, defense, and aerospace fields as coatings, adhesives, and elastomers. However, in the textile field, compared with traditional petroleum-based polyurethane, BWPU still has some performance shortcomings, such as the superimposed contradiction of grain supply, poor water resistance, stain resistance, weather resistance, and relatively complex production processes, which greatly limit its large-scale application in the aforementioned fields. To address this, researchers at home and abroad have conducted extensive research using various preparation techniques and modification methods. The results show that structural regulation, functional group construction, and filler modification can effectively help develop high-performance BWPU (enhancing the hydrophobicity, stain resistance, antibacterial properties, and self-healing properties of materials) and widely replace traditional petroleum-based polyurethane materials.

[0003] Currently, research on enhancing the overall performance of BWPU includes: (1) using bio-based polyols (vegetable oils, lignin, starch, algal oil polyols, etc.) as raw materials and coordinating them with isocyanates, emulsifiers, crosslinking agents, and functional end-capping agents to improve BWPU performance; (2) enhancing BWPU performance through functional chain segment side-linking / blending; and (3) enhancing BWPU performance through the reinforcement and toughening effect of nanofillers. However, due to the harsh functionalization conditions of raw materials, low side-linking rates, and interfacial phase separation between nanofillers and polyurethane matrix in the above preparation methods, BWPU still lags far behind petroleum-based polyurethane in actual large-scale production and application.

[0004] Therefore, it is essential to study the design, process, influencing factors, and protection and enhancement mechanisms of the research route "non-grain bio-based materials - preparation of functionalized polyols - catalyst-free green bio-based polyurethane synthesis process -". Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a jatropha oil-based waterborne polyurethane emulsion. This invention uses jatropha oil as raw material, employs functionalized molecular design, and introduces KH550 through a catalyst-free green chemical process to synthesize a controllable jatropha oil-based polyol. Through chain structure design, it is further polymerized with isophorone diisocyanate to prepare a jatropha oil-based waterborne polyurethane coating dispersion. This dispersion is then applied to the surface of fabrics to form a high-performance coating and enhance the hydrophobic and stain-resistant properties of the fabrics.

[0006] The objective of this invention is achieved through the following technical solution: A method for preparing a jatropha oil-based waterborne polyurethane emulsion includes the following steps: Step 1: Preparation of anhydrous EJO (EJO): Add organic acid to jatropha oil and stir at 280 r / min for 20 min at 40 ℃. After the reactants are mixed evenly, add a certain amount of peroxide dropwise at a uniform rate. After the addition is complete, raise the temperature to 60 ℃ and react for 5 h. After standing and separating into layers, take the upper layer product, wash it with water 3 times, and obtain EJO by rotary evaporation.

[0007] Step 2: Preparation of Jatropha curcas oil-based polyol (Si-JOL): The silane coupling agent and the above-mentioned EJO are thoroughly mixed under an inert gas atmosphere. The mixture is heated to 110°C and reacted for 5-6 hours to obtain Si-JOL.

[0008] ;

[0009] Step 3: Preparation of waterborne polyurethane (Si-WPU) for jatropha oil-based textiles: Under closed conditions, the system was purged three times with an inert gas. A certain amount of Si-JOL and DMPA (pre-dissolved in NMP) were stirred at 250-350 r / min for 30 min at 80℃. Then, a certain amount of isocyanate was added dropwise at a uniform rate. After the addition was complete, 2-3 drops of catalyst were added and the reaction was allowed to proceed for 3 h. After the reaction was complete, HEMA was added and the reaction was allowed to proceed for 1 h. Then, after the temperature was allowed to cool naturally to 40 ℃, TEA was added and the reaction was allowed to proceed for 0.5 h. After the reaction was completed, jatropha oil-based waterborne polyurethane prepolymer was obtained. 20 g of water was added and dispersed at 1000-1200 r / min for 1 h to obtain jatropha oil-based waterborne polyurethane emulsion for textiles.

[0010] Jatropha curcas oil-based waterborne polyurethane emulsion for textiles includes the following components: jatropha curcas oil, organic acids, peroxides, silane coupling agents, 2,2-dimethylolpropionic acid, N-methylpyrrolidone, isocyanate, catalyst, 2-hydroxyethyl methacrylate, triethylamine, and deionized water.

[0011] Furthermore, the organic acid is either formic acid or acetic acid.

[0012] Furthermore, the peroxide is hydrogen peroxide.

[0013] Furthermore, the silane coupling agent is KH550.

[0014] Furthermore, the catalyst is any one of stannous octoate, di(dodecyl sulfide)dibutyltin, dibutyltin diacetate, or dibutyltin laurate.

[0015]

[0016] The prepared Si-WPU was coated onto the surface of a polyamide fabric, which was then placed in an oven and dried at 70 °C for 5 h to obtain a completely dry modified fabric. The static water contact angle was measured using an FCA500B optical contact angle meter. The droplet volume was controlled at 5 µL for each measurement, and the experiment was repeated 5 times. The final result was the average of the 5 measurements.

[0017] The beneficial effects of this invention are: 1. This invention uses green, renewable, non-grain bio-based materials as raw materials, focusing on the technological bottlenecks in the high-value application of non-grain biomass materials in the field of waterborne polyurethane. It prepares functional bio-based polyol materials through green and controllable functionalization synthesis technology, and further prepares high-performance polyurethane to explore the structure-property relationship between the bio-based polyol structure, resin molecular structure, dynamic crosslinking network, and resin properties. This breaks through the path dependence of traditional polyurethane on fossil-based raw materials, effectively reducing the polyurethane industry's dependence on fossil resources, and providing reliable theoretical guidance for the preparation of high-performance bio-based waterborne polyurethane.

[0018] 2. The main innovation of this invention lies in the preparation of functionalized bio-based polyols. It primarily involves introducing functional segments into the polyol preparation process using functional additives through molecular design, thereby imbuing the polyurethane molecular chains with functional groups and endowing the polyurethane with meaningful comprehensive properties.

[0019] 3. This invention breaks through the existing technical barriers of bio-based materials in the field of waterborne coatings for textiles, and expands the application of waterborne bio-based polyurethane emulsions in the textile field. Detailed Implementation

[0020] The present invention will be further described below with reference to the scheme and specific embodiments, so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention. Example 1

[0021] 100 g JO, 13.25 g formic acid, and 73.24 g hydrogen peroxide (30% by mass) were reacted completely for 5 h. After standing and separating into layers, the upper layer was taken and rotary evaporated to obtain EJO. This EJO and silane coupling agent were thoroughly mixed at a mass ratio of 5:2. The mixture was reacted at 110 °C for 5.5 h under nitrogen protection to obtain Si-JOL A. Its hydroxyl value was measured and listed in Table 1. Example 2

[0022] 100 g JO, 13.25 g formic acid, and 73.24 g hydrogen peroxide (30% by mass) were reacted completely for 5 h. After standing and separating into layers, the upper layer was taken and rotary evaporated to obtain EJO. This EJO and KH550 were thoroughly mixed at a mass ratio of 2:1. The mixture was reacted at 110 °C for 5.5 h under nitrogen protection to obtain Si-JOL B. Its hydroxyl value was measured and listed in Table 1. Example 3

[0023] 100 g JO, 13.25 g formic acid, and 73.24 g hydrogen peroxide (30% by mass) were reacted completely for 5 h. After standing and separating into layers, the upper layer was taken and rotary evaporated to obtain anhydrous EJO. This EJO and silane coupling agent were thoroughly mixed at a mass ratio of 5:3. The mixture was reacted at 110 °C for 5.5 h under nitrogen protection to obtain Si-JOL C. The hydroxyl values ​​were measured and listed in Table 1. Example 4

[0024] Under sealed conditions, the system was purged three times with an inert gas. 8.5g of Si-JOL B and 0.83DMPA (pre-dissolved in 20g NMP) were stirred at 80℃ for 30min. Then, 5.4g of isophorone diisocyanate and 3 drops of catalyst were added dropwise, and the reaction was allowed to proceed for 3h. After the reaction was completed, HEMA was added and reacted for 1h. Then, after the temperature was allowed to cool naturally to 40℃, TEA was added and reacted for 0.5h. After the reaction was completed, a jatropha oil-based waterborne polyurethane prepolymer was obtained. 20g of water was added and dispersed for 1h to obtain Si-WPU A. Its properties were tested and listed in Table 2. Example 5

[0025] Under sealed conditions, the system was purged three times with an inert gas. 9 g of Si-JOL polyol B and 0.83 g of DMPA (pre-dissolved in 20 g of NMP) were stirred at 80 °C for 30 min. Then, 5.4 g of isophorone diisocyanate and 3 drops of catalyst were added dropwise, and the reaction was allowed to proceed for 3 h. After the reaction was completed, HEMA was added and reacted for 1 h. Then, after the temperature was allowed to cool naturally to 40 °C, TEA was added and reacted for 0.5 h. After the reaction was completed, jatropha oil-based waterborne polyurethane prepolymer was obtained. 20 g of water was added and dispersed for 1 h to obtain Si-WPU B. Its properties were tested and listed in Table 2. Example 6

[0026] Under sealed conditions, the system was purged three times with an inert gas. 9.5 g of Si-JOL polyol B and 0.83 g of DMPA (pre-dissolved in 20 g of NMP) were stirred at 80 °C for 30 min. Then, 5.4 g of isophorone diisocyanate and 3 drops of catalyst were added dropwise, and the reaction was allowed to proceed for 3 h. After the reaction was completed, HEMA was added and reacted for 1 h. Then, after the temperature was allowed to cool naturally to 40 °C, TEA was added and reacted for 0.5 h. After the reaction was completed, jatropha oil-based waterborne polyurethane prepolymer was obtained. 20 g of water was added and dispersed for 1 h to obtain Si-WPU C. Its properties were tested and listed in Table 2.

[0027] Table 1. Detection results of the examples Component Name Hydroxyl value (mg KOH / g) Example 1 254.68 Example 2 272.99 Example 3 269.32 Table 2 Results of Example Detection Component Name Contact angle / ° Example 4 104.661 Example 5 106.702 Example 6 110.940 .

Claims

1. A method for preparing a jatropha oil-based waterborne polyurethane emulsion, characterized in that, The method includes the following preparation steps: (1) Preparation of epoxy jatropha oil: Organic acid was added to jatropha oil (JO), and the mixture was stirred at 280 r / min for 20 min at 40 ℃. After the reactants were mixed evenly, a certain amount of peroxide was added dropwise at a uniform rate. After the addition was completed, the temperature was raised to 60 ℃ and the reaction was carried out for 5 h. After standing and separating into layers, the upper layer product was washed with water 3 times and rotary evaporated to obtain anhydrous epoxy jatropha oil (EJO). (2) Preparation of aminosilanized jatropha oil-based polyol: The silane coupling agent and the above EJO were thoroughly mixed under an inert gas atmosphere. The mixture was heated to 110 °C and reacted for 5-6 h to obtain aminosilanized jatropha oil-based polyol (Si-JOL). (3) Preparation of waterborne polyurethane for jatropha oil-based textiles: Under closed conditions, the system was purged three times with an inert gas. Si-JOL and 2,2-dimethylolpropionic acid (DMPA) (pre-dissolved in N-methylpyrrolidone (NMP)) were stirred at 250-350 r / min for 30 min at 80 ℃. Then, isocyanate was added dropwise at a uniform rate. After the addition was complete, 2-3 drops of catalyst were added and the reaction was allowed to proceed for 3 h. After the reaction was complete, 2-hydroxyethyl methacrylate (HEMA) was added and the reaction was allowed to proceed for 1 h. Then, after the temperature was allowed to cool naturally to 40 ℃, triethylamine (TEA) was added and the reaction was allowed to proceed for 0.5 h. After the reaction was completed, jatropha oil-based waterborne polyurethane prepolymer was obtained. 20 g of water was added and dispersed at 1000-1200 r / min for 1 h to obtain jatropha oil-based waterborne polyurethane emulsion (Si-WPU) for textiles. (4) The prepared Si-WPU was coated on the surface of the polyamide fabric and then placed in an oven and dried at 70 °C for 5 h to obtain a completely dry modified fabric. The static water contact angle was measured using an FCA500B optical contact angle measuring instrument. The droplet volume was controlled at 5 µL for each measurement. The experiment was repeated 5 times, and the final result was the average of the 5 measurements.

2. The method for preparing a jatropha oil-based waterborne polyurethane emulsion according to claim 1, characterized in that, In step (1) above, the organic acid is formic acid or acetic acid; the peroxide is hydrogen peroxide with a mass fraction of 30%.

3. The method for preparing a jatropha oil-based waterborne polyurethane emulsion according to claim 1, characterized in that, In step (2) above, the inert gas is argon or nitrogen; the silane coupling agent is KH550; and the mass ratio of the silane coupling agent to EJO is 2~3:

5.

4. The method for preparing a jatropha oil-based waterborne polyurethane emulsion according to claim 1, characterized in that, In step (3) above, the inert gas is argon or nitrogen; the isocyanate is one of diphenylmethane diisocyanate, toluene diisocyanate, or isophorone diisocyanate; and the catalyst is one of stannous octoate, di(dodecyl sulfide)dibutyltin, dibutyltin diacetate, or dibutyltin laurate.

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