Anti-yellowing antistatic agent as well as preparation method and application thereof
A sulfonate and phosphate ester-based anti-static agent with castor oil segments addresses yellowing and thermal instability issues, ensuring effective anti-static performance and compatibility with polyurethane materials.
Patent Information
- Application Number
- CN202510550488.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-29
- Publication Date
- 2025-07-15
AI Technical Summary
Existing antistatic agents are prone to discoloration in high temperature environments, affecting the transparency of the material, and lack compatibility with polyurethane materials and antistatic properties.
Antistatic agents containing sulfonate groups, phosphate groups and castor oil segments are used to react with modified castor oil and phosphorus pentoxide to form antistatic agents containing sulfonate and phosphate salts, which enhance antistatic properties and improve compatibility by reacting hydroxyl groups on castor oil with polyurethane.
Both have excellent antistatic properties under dry and wet conditions, good heat resistance, not easy to yellow, and have good compatibility with polyurethane materials, maintaining a long-lasting antistatic effect.
Smart Images
Figure CN120309801A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of antistatic agents, and particularly to an antistatic agent that is not prone to yellowing, and a preparation method and application thereof. Background Art
[0002] Antistatic agents are a class of chemical substances or mixtures used to reduce or prevent the generation of static electricity on objects. They prevent or reduce the generation of static electricity by changing the conductivity of the object. The main function of antistatic agents is to reduce the surface resistance and volume resistance of materials or products, moderately improve the conductivity, and prevent the accumulation of static electricity. Common antistatic agents on the market are classified by ion type into anionic antistatic agents, cationic antistatic agents, zwitterionic antistatic agents, and nonionic antistatic agents. Cationic antistatic agents mainly include various amine salts, quaternary ammonium salts, and alkyl imidazoline salts, etc., among which quaternary ammonium salts are the most widely used. However, most cationic antistatic agents are nitrogen-containing compounds and are prone to color change in high-temperature environments, affecting the transparency of the material. Zwitterionic antistatic agents mainly include amino acid type, betaine type, and imidazoline type. Similar to cationic surfactants, since zwitterionic surfactants contain nitrogen elements, they are prone to color change in high-temperature environments. Nonionic antistatic agents mainly include poly(ethylene oxide) alkyl ethers, poly(ethylene oxide) alkyl phenyl ethers, fatty acid esters of sorbitan, etc. Nonionic antistatic agents have poor adsorption to fibers and cannot ionize themselves, so the antistatic effect is poor. Anionic antistatic agents mainly include sulfonates and phosphate esters, etc. Their antistatic effect is good, but their compatibility with polymer materials is poor, making them prone to decomposition and precipitation during the high-temperature processing of polyurethane materials, resulting in phenomena such as oil bleeding, blooming, and delamination on the product surface. Therefore, it is necessary to improve their heat resistance and compatibility with polyurethane materials.
[0003] Patent CN1063985851B provides an antistatic agent for adhesives. The antistatic agent for adhesives contains a quaternary ammonium salt cation part and a bis(fluorosulfonyl)imide anion part, and has excellent durability under high-temperature and high-humidity conditions. The antistatic agent for adhesives of this invention can be widely used in adhesive polymers such as (meth)acrylic polymers, rubber polymers, silicone polymers, and polyurethane polymers. However, a large amount of quaternary ammonium salt structure in this antistatic agent is prone to decomposition under high-temperature conditions, making the antistatic effect of the binder worse.
[0004] Patent CN118420853B provides a preparation method of a hydrophobic antistatic polyurethane, including the following steps: mixing a polyurethane intermediate B containing double bonds and fluorine, conductive carbon black modified with a silane coupling agent, a metal framework material, isopropyl alcohol, water, and a photoinitiator Irgacure184 evenly to obtain a hydrophobic antistatic polyurethane. However, this antistatic agent may affect the coloring of the product, limiting its application in products that require specific colors.
[0005] Therefore, there is an urgent need in the market to develop an antistatic agent with excellent antistatic performance, good heat resistance, good compatibility with polyurethane materials, and not prone to yellowing. Summary of the Invention
[0006] Aiming at the problems existing in the prior art, the purpose of the present invention is to develop an antistatic agent with excellent antistatic performance, applicable in both dry and wet conditions, good heat resistance, good compatibility with polyurethane, and not prone to yellowing.
[0007] In order to achieve the above purpose, the technical solutions adopted by the present invention are as follows:
[0008] In the first aspect of the present invention, an antistatic agent not prone to yellowing is provided, and the structural formula of the antistatic agent not prone to yellowing is as follows:
[0009]
[0010] Among them, X is an integer from 1 to 4, and Y is an integer from 1 to 5.
[0011] The present application has developed an antistatic agent not prone to yellowing, which contains sulfonate groups, phosphate ester groups, and castor oil segments, enabling the antistatic agent not prone to yellowing to have good antistatic performance in both dry and wet conditions. And this antistatic agent not prone to yellowing contains carbon-nitrogen triple bonds, benzene rings, and double bond structures, and has better heat resistance compared with conventional dispersants. The partial hydroxyl groups carried on the castor oil can improve the ability of the antistatic agent molecules to absorb moisture under dry conditions, thereby facilitating the improvement of the antistatic performance of the antistatic agent under dry conditions. And the residual hydroxyl groups on the castor oil can have good reaction performance with the isocyanate groups on the polyurethane, which can prevent the antistatic agent from precipitating, and further improve its compatibility with polyurethane materials, so that the antistatic agent has a lasting antistatic effect.
[0012] In the second aspect of the present invention, a preparation method of an antistatic agent not prone to yellowing is provided, which includes the following steps:
[0013] A1. Add acrylonitrile, sodium p-styrenesulfonate, and castor oil into acetonitrile, stir at room temperature for 20 - 30 min, add an initiator, and stir at 65 - 75 °C for 2 - 4 h, then perform rotary evaporation and drying to obtain modified castor oil;
[0014] A2. Add the modified castor oil obtained in step A1 into deionized water, heat up to 55 - 65 °C, and stir for 20 - 30 min to obtain an aqueous solution;
[0015] A3. Add phosphorus pentoxide into fatty alcohol polyoxyethylene ether phosphate, stir at room temperature for 20 - 30 min to obtain a mixture;
[0016] A4. Add the mixture obtained in step A3 to the aqueous solution obtained in step A2, react at 50 - 70 °C for 4 - 6 h, add deionized water, continue to react for 1 - 2 h, add a 13 - 16 wt% sodium hydroxide aqueous solution, adjust the pH to 7 - 9, continue to react for 30 - 60 min, filter by suction, precipitate the filtrate with ethanol and then wash with acetone, and obtain an anti - static agent that is not prone to yellowing after vacuum drying.
[0017] Sulfonate - type anti - static agents are relatively lower in price compared to phosphate - type anti - static agents. Phosphate - type anti - static agents can not only provide antistatic properties but also impart a certain lubricity to the material surface, reduce the friction coefficient, thereby inhibiting and reducing the generation of static charges. At the same time, they can also improve the bundling property of polyurethane materials. In this application, by reacting a modified castor oil containing a sulfonate group with phosphorus pentoxide to form an anti - static agent containing both sulfonate groups and phosphate groups, the advantages of sulfonates and phosphates can be combined to play a synergistic role, reduce the dependence of the anti - static agent on a humid environment and is conducive to improving its heat resistance. And some hydroxyl groups still remain on the castor oil chain segment, which is not only beneficial for absorbing moisture in the air but also can react with polyurethane to prevent the anti - static agent from precipitating, thereby enabling the anti - static agent to have a lasting antistatic effect.
[0018] In some embodiments, the fatty alcohol polyoxyethylene ether phosphate is AEO - 3 phosphate.
[0019] In some embodiments, the mass ratio of the castor oil to acrylonitrile is 1:(0.05 - 0.23).
[0020] In some embodiments, the mass ratio of the castor oil to sodium p - styrenesulfonate is 1:(0.22 - 1).
[0021] In some embodiments, the mass ratio of the castor oil to acetonitrile is 1:(1.5 - 2.5).
[0022] In this application, by limiting the ratios of castor oil to acrylonitrile, castor oil to sodium p - styrenesulfonate, and castor oil to acetonitrile, the antistatic performance of the anti - static agent can be improved. This may be because under this ratio, sufficient hydrophilic groups can still be retained on the castor oil chain segment, which is beneficial for absorbing moisture in the air and improving the antistatic effect of the anti - static agent under dry conditions. And the remaining partial hydroxyl groups on the castor oil can react with polyurethane, which is beneficial for improving the dispersibility and heat - resistant performance of the anti - static agent, further enhancing the antistatic performance of the material. And the appropriate number of active hydroxyl groups carried on this anti - static agent will not affect the curing process of polyurethane.
[0023] In some embodiments, the mass ratio of the modified castor oil to deionized water in step A2 is 1:(2 - 4).
[0024] In some embodiments, the mass ratio of phosphorus pentoxide to fatty alcohol polyoxyethylene ether phosphate is 1:(0.1 - 0.4).
[0025] In some embodiments, the mass ratio of the mixture to the aqueous solution in step A4 is 1:(5 - 8).
[0026] By defining the ratios of modified castor oil to deionized water, phosphorus pentoxide to fatty alcohol polyoxyethylene ether phosphate, and the mixture to the aqueous solution, the antistatic agent of the present application can have good antistatic performance. This may be because the modified castor oil in the aqueous solution obtained according to this ratio has good dispersibility, which makes the hydroxyl groups easily exposed to react with phosphorus pentoxide, thereby improving the antistatic performance.
[0027] The third aspect of the present invention provides an application of an antistatic agent that is not easily yellowed. The addition amount when used for polyurethane is 1 - 2 wt%.
[0028] Compared with the prior art, the present invention has the following beneficial effects:
[0029] 1. The present invention develops an antistatic agent that is not easily yellowed, which contains sulfonate groups, phosphate groups, and castor oil segments, enabling the antistatic agent that is not easily yellowed to have good antistatic performance under both dry and wet conditions. Moreover, the antistatic agent that is not easily yellowed contains carbon-nitrogen triple bonds, benzene rings, and double bond structures, and has better heat resistance compared to conventional dispersants. Additionally, the antistatic agent has good compatibility with polyurethane.
[0030] 2. By reacting modified castor oil containing sulfonate groups with phosphorus pentoxide, the present invention forms an antistatic agent that simultaneously contains sulfonate groups and phosphate groups, which can integrate the advantages of sulfonate and phosphate groups. Moreover, some hydrophilic groups are still retained on the castor oil segments, which is beneficial for absorbing moisture in the air and enhancing the antistatic effect of the antistatic agent. And the remaining hydroxyl groups, etc., can react with polyurethane to prevent the antistatic agent from precipitating, thereby enabling the antistatic agent to have a long-lasting antistatic effect.
[0031] 3. When the antistatic agent prepared by the present invention is used for polyurethane materials, the addition amount is 1 - 2 wt%, which can prevent polyurethane from yellowing and ensure its transparency. Description of the Drawings
[0032] Figure 1 1H NMR spectrum of the antistatic agent that is not easily yellowed prepared in Example 1. Detailed Embodiments
[0033] The present invention will be described below in conjunction with specific implementation embodiments. It should be noted that the following embodiments are examples of the present invention, which are only used to illustrate the present invention and not to limit the present invention. Other combinations and various improvements within the concept of the present invention can be made without departing from the gist or scope of the present invention.
[0034] In the following examples, the compounds and related reagents used are all commercially available. Among them, castor oil is purchased from Jinan Qingtian Chemical Technology Co., Ltd.; the polyurethane is BASF one-component polyurethane LR9100; AEO-3 phosphate is purchased from Jiangsu Haian Petrochemical Factory.
[0035] The instrument used is a nuclear magnetic resonance hydrogen spectrum, and the radio frequency is 600M.
[0036] Example 1
[0037] A method for preparing an anti-static agent that is not easily yellowed, comprising the following steps:
[0038] A1. Add 1.4 g of acrylonitrile, 6.1 g of sodium p-styrenesulfonate, and 10 g of castor oil to 20 g of acetonitrile, stir at room temperature for 25 min, add 0.1 g of azobisisobutyronitrile, stir at 70 °C for 3 h, perform rotary evaporation and drying to obtain modified castor oil;
[0039] A2. Add 10 g of the modified castor oil obtained in step A1 to 30 g of deionized water, heat up to 60 °C and stir for 25 min to obtain an aqueous solution;
[0040] A3. Add 10 g of phosphorus pentoxide to 2.5 g of AEO-3 phosphate, stir at room temperature for 25 min to obtain a mixture;
[0041] A4. Add 10 g of the mixture obtained in step A3 to 65 g of the aqueous solution obtained in step A2, react at 60 °C for 5 h, add 50 g of deionized water, continue to react for 1.5 h, add a 15 wt% sodium hydroxide aqueous solution, adjust the pH to 8, continue to react for 45 min, perform suction filtration, precipitate the filtrate with ethanol, wash with acetone, and perform vacuum drying to obtain an anti-static agent that is not easily yellowed. The structural formula of the anti-static agent is as follows:
[0042]
[0043] Among them, X is 2 and Y is 3.
[0044] Figure 11H-NMR test chart of the anti-static agent with poor yellowing prepared in Example 1. The peaks at ~7.38 and 7.78 ppm are the proton peaks of the benzene ring on the sodium p-styrenesulfonate segment. The peak at about ~2.57 ppm is the proton peak on the acrylonitrile segment. The peak at ~4.34 ppm is the proton peak on the carbon connected to the phosphate ester salt on the castor oil segment. The peak near ~5.40 is the proton peak on the double bond of castor oil, confirming that the anti-static agent containing sulfonate group, phosphate ester salt group and castor oil segment is successfully synthesized in this application.
[0045] Example 2
[0046] A preparation method of an anti-static agent with poor yellowing, comprising the following steps:
[0047] A1. Add 0.5 g of acrylonitrile, 2.2 g of sodium p-styrenesulfonate and 10 g of castor oil into 15 g of acetonitrile, stir at room temperature for 20 min, add 0.1 g of azobisisobutyronitrile, and stir at 65 °C for 4 h. After rotary evaporation and drying, modified castor oil is obtained.
[0048] A2. Add 10 g of the modified castor oil obtained in step A1 into 20 g of deionized water, and raise the temperature to 55 °C and stir for 30 min to obtain an aqueous solution.
[0049] A3. Add 10 g of phosphorus pentoxide into 1 g of AEO-3 phosphate ester, and stir at room temperature for 20 min to obtain a mixture.
[0050] A4. Add 10 g of the mixture obtained in step A3 into 50 g of the aqueous solution obtained in step A2, react at 50 °C for 6 h, add 50 g of deionized water, continue to react for 2 h, add 15 wt% sodium hydroxide aqueous solution, adjust the pH to 7, continue to react for 60 min, filter by suction, precipitate the filtrate with ethanol and then wash with acetone, and obtain the anti-static agent with poor yellowing after vacuum drying.
[0051] Example 3
[0052] A preparation method of an anti-static agent with poor yellowing, comprising the following steps:
[0053] A1. Add 2.3 g of acrylonitrile, 10 g of sodium p-styrenesulfonate and 10 g of castor oil into 25 g of acetonitrile, stir at room temperature for 30 min, add 0.1 g of azobisisobutyronitrile, and stir at 75 °C for 2 h. After rotary evaporation and drying, modified castor oil is obtained.
[0054] A2. Add 10 g of the modified castor oil obtained in step A1 into 40 g of deionized water, and raise the temperature to 65 °C and stir for 20 min to obtain an aqueous solution.
[0055] A3. Add 10 g of phosphorus pentoxide into 4 g of AEO-3 phosphate ester, and stir at room temperature for 30 min to obtain a mixture.
[0056] A4. Add 10 g of the mixture obtained in step A3 to 80 g of the aqueous solution obtained in step A2, react at 70 °C for 4 h, add 50 g of deionized water, continue to react for 1 h, add a 15 wt% aqueous sodium hydroxide solution, adjust the pH to 9, continue to react for 30 min, perform suction filtration, precipitate the filtrate with ethanol and then wash with acetone, and obtain an anti-static agent that is not easily yellowed after vacuum drying.
[0057] Example 4
[0058] A preparation method of an anti-static agent that is not easily yellowed. The specific implementation method is the same as that of Example 1, except that the addition amount of acrylonitrile is 3 g.
[0059] Example 5
[0060] A preparation method of an anti-static agent that is not easily yellowed. The specific implementation method is the same as that of Example 1, except that the addition amount of sodium p-styrenesulfonate is 1 g.
[0061] Example 6
[0062] A preparation method of an anti-static agent that is not easily yellowed. The specific implementation method is the same as that of Example 1, except that the addition amount of acetonitrile is 10 g.
[0063] Example 7
[0064] A preparation method of an anti-static agent that is not easily yellowed. The specific implementation method is the same as that of Example 1, except that the addition amount of deionized water in step A2 is 10 g.
[0065] Example 8
[0066] A preparation method of an anti-static agent that is not easily yellowed. The specific implementation method is the same as that of Example 1, except that the addition amount of the aqueous solution in step A4 is 40 g.
[0067] Comparative Example 1
[0068] A preparation method of an anti-static agent that is not easily yellowed, comprising the following steps: Add 1.4 g of acrylonitrile, 6.1 g of sodium p-styrenesulfonate and 10 g of castor oil to 20 g of acetonitrile, stir at room temperature for 25 min, add 0.1 g of azobisisobutyronitrile, stir at 70 °C for 3 h, perform rotary evaporation and drying to obtain an anti-static agent that is not easily yellowed.
[0069] Comparative Example 2
[0070] A preparation method of an anti-static agent that is not easily yellowed, comprising the following steps:
[0071] A1. Add 1.4 g of acrylonitrile and 10 g of castor oil to 20 g of acetonitrile, stir at room temperature for 25 min, add 0.1 g of azobisisobutyronitrile, stir at 70 °C for 3 h, rotary evaporate and dry to obtain modified castor oil;
[0072] A2. Add 10 g of phosphorus pentoxide to 2.5 g of AEO-3 phosphate ester, stir at room temperature for 25 min to obtain a mixture;
[0073] A3. Add 1 g of the mixture obtained in step A2 to 6.5 g of the modified castor oil obtained in step A1, react at 60 °C for 5 h, add 10 g of deionized water, continue to react for 1.5 h, add 15 wt% sodium hydroxide aqueous solution, adjust the pH to 8, continue to react for 45 min, filter by suction, precipitate the filtrate with ethanol and then wash with acetone, and vacuum dry to obtain an anti-static agent that is not easily yellowed.
[0074] Performance Test
[0075] (1) Specimen Preparation
[0076] According to the prior art, add the anti-static agent that is not easily yellowed obtained in each example to polyurethane at a dosage of 1.5 wt% to obtain various samples, and cut each sample into specimens with a length of 125 ± 5 mm and a width of 13 ± 0.5 mm.
[0077] (2) Performance Test
[0078] 1. Antistatic performance under dry and wet conditions: Use a high-resistance meter to measure the surface resistivity of each specimen under the conditions of 20 °C × 65% RH and 20 °C × 20% RH respectively;
[0079] 2. Durability: Place each specimen in the condition of 200 °C × 20% RH, and measure the surface resistivity of each specimen after 10 h.
[0080] The test results are shown in Table 1:
[0081] Table 1
[0082]
[0083] As can be seen from the data in Table 1, the antistatic agents with good yellowing resistance prepared in Examples 1-3 have good antistatic performance under both dry and wet conditions and excellent heat resistance. From the comparison between Examples 4, 5, 6 and Example 1, it can be seen that after changing the ratio of castor oil to acrylonitrile, castor oil to sodium p-styrenesulfonate, or castor oil to acetonitrile, the hydrophilic groups remaining on the antistatic agent decrease, resulting in poor antistatic performance of the antistatic agent under dry conditions and the remaining hydroxyl groups on the antistatic agent being less likely to react with polyurethane, leading to poor compatibility between the antistatic agent and the polyurethane material and thus a decrease in the high-temperature resistance of the antistatic agent and a decline in the antistatic performance of the polyurethane material. From the comparison between Examples 7, 8 and Example 1, it can be seen that after changing the ratio of modified castor oil to deionized water or the mixture and aqueous solution, the poor dispersibility of the modified castor oil makes it difficult to graft phosphate salt groups onto the antistatic agent, resulting in a decrease in the antistatic performance of the polyurethane material. From the comparison between Comparative Examples 1, 2 and Example 1, it can be seen that the antistatic agents without phosphate salt groups or without sulfonate groups have poor antistatic performance.
[0084] The above embodiments are only for illustrating the technical concept and characteristics of the present invention, and the purpose is to enable those familiar with this technology to understand the content of the present invention and implement it. However, the protection scope of the present invention cannot be limited thereby. Any equivalent changes or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.
Claims
1. An antistatic agent that is not easily yellowed, characterized in that, The structural formula of the anti-static agent that is not easily yellowed is as follows: Among them, X is an integer from 1 to 4, and Y is an integer from 1 to 5.
2. A method for preparing the antistatic agent with poor yellowing resistance according to claim 1, characterized in that, It includes the following steps: A1. Add acrylonitrile, sodium p-styrenesulfonate, and castor oil into acetonitrile, stir at room temperature for 20 - 30 min, add an initiator, stir at 65 - 75 °C for 2 - 4 h, perform rotary evaporation and drying to obtain modified castor oil; A2. Add the modified castor oil obtained in step A1 into deionized water, heat up to 55 - 65 °C and stir for 20 - 30 min to obtain an aqueous solution; A3. Add phosphorus pentoxide into fatty alcohol polyoxyethylene ether phosphate, stir at room temperature for 20 - 30 min to obtain a mixture; A4. Add the mixture obtained in step A3 into the aqueous solution obtained in step A2, react at 50 - 70 °C for 4 - 6 h, add deionized water, continue to react for 1 - 2 h, add a 13 - 16 wt% sodium hydroxide aqueous solution, adjust the pH to 7 - 9, continue to react for 30 - 60 min, perform suction filtration, precipitate the filtrate with ethanol and then wash with acetone, and perform vacuum drying to obtain the anti-static agent that is not easily yellowed.
3. The preparation method of the anti-static agent with poor yellowing resistance according to claim 2, characterized in that, The fatty alcohol polyoxyethylene ether phosphate is AEO-3 phosphate.
4. The preparation method of the antistatic agent with poor yellowing resistance according to claim 2, characterized in that, The mass ratio of the castor oil to acrylonitrile is 1:(0.05 - 0.23).
5. The preparation method of the antistatic agent with low yellowing tendency according to claim 2, wherein, The mass ratio of the castor oil to sodium p-styrenesulfonate is 1:(0.22 - 1).
6. The preparation method of the antistatic agent with poor yellowing resistance according to claim 2, characterized in that, The mass ratio of the castor oil to acetonitrile is 1:(1.5 - 2.5).
7. The preparation method of the antistatic agent with poor yellowing resistance according to claim 2, characterized in that, In step A2, the mass ratio of the modified castor oil to deionized water is 1:(2 - 4).
8. The preparation method of the antistatic agent with poor yellowing resistance according to claim 2, characterized in that The mass ratio of the phosphorus pentoxide to the fatty alcohol polyoxyethylene ether phosphate is 1:(0.1 - 0.4).
9. The preparation method of the anti-static agent with poor yellowing resistance according to claim 2, characterized in that, In step A4, the mass ratio of the mixture to the aqueous solution is 1:(5 - 8).
10. Use of an anti-static agent that does not easily turn yellow as described in claim 1 or an anti-static agent that does not easily turn yellow obtained by the preparation method described in any one of claims 2-9, characterized in that, The addition amount when used for polyurethane is 1 - 2 wt%.