Preparation method and application of alkyl organic phosphine antistatic agent

Abstract

The invention discloses a preparation method and application of an alkyl organic phosphine antistatic agent, and belongs to the technical field of antistatic agents. The antistatic agent prepared by the invention is octyl phosphonic acid monoethyl ester potassium. The preparation method comprises the following steps: reacting raw materials 1-bromooctane with triethyl phosphite in a microreactor; carrying out reduced pressure distillation to obtain an intermediate product diethyl octyl phosphonate; and then carrying out ester hydrolysis reaction with a KOH aqueous solution to prepare the alkyl organic phosphine antistatic agent. The stainless steel microreactor with the inner diameter of 2mm and the effective length of 5m is innovatively adopted, compared with a traditional reaction system, the yield of an intermediate is increased by 11% and can reach 98% at most, and toxic raw materials such as phosphorus oxychloride are prevented from being used. The alkyl organic phosphine antistatic agent prepared by the invention can reduce the specific resistance of fibers from 1013 omega.cm to 107 omega.cm magnitude, has the advantages of efficient mass transfer, environmental protection and excellent antistatic performance, and is suitable for the fields of textiles, plastics and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of antistatic agents, in particular to a preparation method and application of an alkyl organic phosphine antistatic agent. Background Art

[0002] With the rapid development of electronics, communications, and military fields, static electricity (ESD) has become an increasingly prominent issue. The accumulation and discharge of static electricity not only negatively impacts product quality and reduces production efficiency, but can also lead to serious safety hazards such as fires and explosions. Therefore, the development of highly effective antistatic agents is crucial for ensuring production safety and improving product performance.

[0003] Antistatic agents primarily eliminate static electricity by improving the conductivity of materials. Commonly used antistatic agents can be divided into two categories: external antistatic agents and internal antistatic agents. External antistatic agents primarily achieve their antistatic effect through surface coating. Potassium monoethyl octylphosphonate, a new phosphonate antistatic agent, exhibits excellent antistatic properties and good compatibility. The long-chain alkyl group in the compound's molecular structure provides good compatibility, while the phosphate group imparts excellent conductivity.

[0004] Alkylphosphonate antistatic agents not only have good antistatic properties, but also have properties such as emulsification, rust prevention and dispersion, and are widely used. They can be used not only in the textile field, but also as antistatic agents for leather and plastics. Its main components include monoesters and diesters, wherein the antistatic properties of monoesters are better than diesters. Diesters can give fabrics excellent smoothness, reduce the coefficient of friction, and help alleviate the generation of static electricity. At present, the synthesis methods of alkylphosphonates are mostly applicable to the synthesis of monoesters or containing the same alkyl diester, and there are few reports on the method for synthesizing phosphonates substituted with different alkyl groups. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention provides a method for preparing and applying an alkyl organophosphine antistatic agent. Using triethyl phosphite, 1-bromooctane, and potassium hydroxide as raw materials, the present invention synthesizes a phosphonate salt containing two different alkyl chains, one ethoxy and one octyl, namely potassium monoethyl octylphosphonate, which exhibits excellent antistatic properties.

[0006] The technical solutions of the present invention are as follows:

[0007] A method for preparing an alkyl organic phosphine antistatic agent, wherein the alkyl organic phosphine antistatic agent is potassium monoethyl octylphosphonate; the chemical structural formula of potassium monoethyl octylphosphonate is as follows:

[0008]

[0009] The preparation method comprises the following steps:

[0010] (1) 1-bromooctane and triethyl phosphite are mixed in equal molar ratios, transported to a microreactor at a constant flow rate using a horizontal flow pump, and reacted under an oil bath;

[0011] (2) After the reaction is completed, 1-bromoethane, unreacted 1-bromooctane and triethyl phosphite are distilled off under reduced pressure to obtain the intermediate product diethyl octylphosphonate;

[0012] (3) adding the intermediate product and a KOH aqueous solution into a reaction vessel to carry out an ester hydrolysis reaction, and after the reaction is completed, obtaining the alkyl organic phosphine antistatic agent.

[0013] Furthermore, in step (1), the microreactor is a microreactor processed into a coil style by a stainless steel capillary with an inner diameter of 2 mm and an outer diameter of 3 mm; the effective length of the microreactor is 5 m, and the effective length is the length of the stainless steel capillary part immersed in the oil bath.

[0014] Furthermore, in step (1), the flow rate is 65-130 μL / min; the temperature of the reaction in the oil bath is 170-190° C., and the reaction time is 2-4 h.

[0015] Furthermore, in step (2), the temperature of the reduced pressure distillation is 100-140° C., and the time is 6-12 h.

[0016] Furthermore, in step (3), the mass concentration of KOH in the KOH aqueous solution is 20-30%; and the molar ratio of the intermediate product to KOH is 1:1-1.3.

[0017] Furthermore, in step (3), the temperature of the ester hydrolysis reaction is 115-130° C., and the time is 4-8 hours.

[0018] The beneficial technical effects of the present invention are:

[0019] This invention innovatively incorporates a tubular microreactor as a reaction device for synthesizing intermediates. Compared to traditional methods of direct mixing and reaction in a flask, this improves the heat and mass transfer efficiency of the reaction, thereby increasing the yield of the intermediate prepared in the first step. In this method, the intermediate product, diethyl octylphosphonate, reached a maximum yield of 98%, an 11% increase compared to the traditional method of direct preparation in a three-necked flask. This method also offers significant advantages in terms of large-scale production, cost-effectiveness, and product consistency.

[0020] Phosphorus oxychloride (such as GB2335920A, CN201910028968.8, and CN202410699859.X) is used in the preparation of traditional antistatic active agents. Compared with the traditional method of using phosphorus oxychloride to synthesize phosphonic acid diesters, the reagents used in the synthesis steps of the present invention and the by-products obtained by the reaction are low-toxic and harmless. Toxic and corrosive raw materials such as phosphorus oxychloride are not used, and irritating and corrosive by-products such as HCl are not produced.

[0021] The product synthesized by the present invention, potassium monoethyl octylphosphonate, has good antistatic and soft properties. The octyl chain is tightly adsorbed on the fiber surface by van der Waals force. The ethoxy group and K + Ion pairs dissociate under the action of water molecules, generating mobile charge carriers and forming conductive channels. This product can be used as an excellent antistatic agent for fabrics. Compared with potassium monoethyl octylphosphonate prepared by traditional synthesis methods, the product prepared by the present invention has better antistatic properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The infrared spectra of the intermediate diethyl octylphosphonate and the product potassium monoethyl octylphosphonate prepared in Example 1 of the present invention are shown.

[0023] Figure 2 The mass spectrum of potassium monoethyl octylphosphonate obtained in Example 1 of the present invention is shown in FIG.

[0024] Figure 3 Schematic diagram of the device of the microreactor of the present invention. DETAILED DESCRIPTION

[0025] The present invention will be described in detail below with reference to the accompanying drawings and embodiments.

[0026] The device diagram of the microreactor described in the following embodiment of the present invention is as follows Figure 3 As shown in the figure, the key components of the device include a horizontal flow pump, an oil bath, and a custom-made stainless steel microchannel. The working principle is as follows: the horizontal flow pump is responsible for transporting the precursor solution into the microreactor at a constant flow rate. The oil bath is used to provide energy for the entire reaction. Stainless steel capillaries with an inner diameter of 2mm and an outer diameter of 3mm are processed into a coiled tube to serve as tubular microreactors. The effective length of the tubular microreactor (5m) is the length of the portion of the stainless steel capillary immersed in the oil bath. During the experiment, the treated precursor solution is placed in a conical flask for later use. After setting the appropriate reaction temperature and reaction flow rate, the precursor solution enters the microreactor via the horizontal flow pump. After the solution flows through the microreactor, the product is obtained and collected in a conical flask for later use.

[0027] Example 1

[0028] A method for preparing an alkyl organic phosphine antistatic agent comprises the following steps:

[0029] (1) 0.2 mol of 1-bromooctane and 0.2 mol of triethyl phosphite were mixed uniformly and transported into the microreactor at a constant flow rate of 87 μL / min using a horizontal flow pump. The mixed raw materials were reacted in an oil bath at 180°C for 3 h under the control of the flow rate of 87 μL / min.

[0030] (2) After the reaction, the temperature was lowered to 120° C. and distilled under reduced pressure for 8 h to separate 1-bromoethane, unreacted 1-bromooctane, and triethyl phosphite, thereby obtaining 0.196 mol of the intermediate product, diethyl octylphosphonate.

[0031] (3) 0.1 mol of diethyl octylphosphonate was added to a three-necked flask, and 20.57 g of a 30% KOH aqueous solution was added dropwise at 120° C. under magnetic stirring. The ester was then hydrolyzed at 120° C. for 6 h. After the reaction was completed, the organic phosphine antistatic agent potassium monoethyl octylphosphonate was obtained.

[0032] Example 2

[0033] A method for preparing an alkyl organic phosphine antistatic agent comprises the following steps:

[0034] (1) 0.2 mol of 1-bromooctane and 0.2 mol of triethyl phosphite were mixed in equal molar ratios and delivered to the microreactor using a horizontal flow pump at a constant flow rate of 65 μL / min. The mixed raw materials were reacted in an oil bath at 170°C for 4 h at a controlled flow rate of 65 μL / min.

[0035] (2) After the reaction, the temperature was lowered to 100°C and distilled under reduced pressure for 6 hours to separate 1-bromoethane, unreacted 1-bromooctane and triethyl phosphite, and 0.193 mol of the intermediate product diethyl octylphosphonate was obtained.

[0036] (3) 0.1 mol of diethyl octylphosphonate was added to a three-necked flask, and 29.17 g of a 25% KOH aqueous solution was added dropwise at 115° C. under magnetic stirring. The ester was then hydrolyzed at 115° C. for 4 h. After the reaction was completed, the organic phosphine antistatic agent potassium monoethyl octylphosphonate was obtained.

[0037] Example 3

[0038] A method for preparing an alkyl organic phosphine antistatic agent comprises the following steps:

[0039] (1) 0.2 mol of 1-bromooctane and 0.2 mol of triethyl phosphite were mixed in equal molar ratios and transported into the microreactor using a horizontal flow pump at a constant flow rate of 87 μL / min. The mixed raw materials were reacted in an oil bath at 190°C for 3 h under the control of the flow rate of 87 μL / min.

[0040] (2) After the reaction, the temperature was lowered to 140° C. and distilled under reduced pressure for 10 h to separate 1-bromoethane, unreacted 1-bromooctane, and triethyl phosphite, thereby obtaining 0.191 mol of the intermediate product, diethyl octylphosphonate.

[0041] (3) 0.1 mol of diethyl octylphosphonate was added to a three-necked flask, and 33.66 g of a 20% KOH aqueous solution was added dropwise under magnetic stirring at 125° C., and then the ester was hydrolyzed at 125° C. for 8 h. After the reaction was completed, the organic phosphine antistatic agent potassium monoethyl octylphosphonate was obtained.

[0042] Example 4

[0043] A method for preparing an alkyl organic phosphine antistatic agent comprises the following steps:

[0044] (1) 0.2 mol of 1-bromooctane and 0.2 mol of triethyl phosphite were mixed in equal molar ratios and transported into the microreactor at a constant flow rate of 131 μL / min using a horizontal flow pump. The mixed raw materials were reacted in an oil bath at 180°C for 2 h under the control of the flow rate of 131 μL / min.

[0045] (2) After the reaction, the temperature was lowered to 130° C. and distilled under reduced pressure for 12 h to separate 1-bromoethane, unreacted 1-bromooctane, and triethyl phosphite, thereby obtaining 0.193 mol of the intermediate product, diethyl octylphosphonate.

[0046] (3) 0.1 mol of diethyl octylphosphonate was added to a three-necked flask, and 36.4 g of a 20% KOH aqueous solution was added dropwise at 130° C. under magnetic stirring. The ester was then hydrolyzed at 130° C. for 6 h. After the reaction, the organic phosphine antistatic agent potassium monoethyl octylphosphonate was obtained.

[0047] Comparative Example 1

[0048] A method for preparing an alkyl organic phosphine antistatic agent comprises the following steps:

[0049] (1) 0.2 mol of 1-bromooctane and 0.2 mol of triethyl phosphite were mixed in equal molar ratios, dissolved in 152 mL of DMSO, and delivered to the microreactor using a horizontal flow pump at a constant flow rate of 87 μL / min. The mixed liquid was reacted in an oil bath at 180°C for 3 h at a controlled flow rate of 87 μL / min.

[0050] (2) After the reaction, the mixture was extracted with methanol, heated to 120°C and distilled under reduced pressure for 8 h to separate the solvent DMSO, methanol, 1-bromoethane, unreacted 1-bromooctane and triethyl phosphite, and 0.165 mol of the intermediate product diethyl octylphosphonate was obtained.

[0051] (3) 0.1 mol of diethyl octylphosphonate was added to a three-necked flask, and 20.57 g of a 30% KOH aqueous solution was added dropwise at 120° C. under magnetic stirring. The ester was then hydrolyzed at 120° C. for 6 h. After the reaction, the organic phosphine antistatic agent potassium monoethyl octylphosphonate was obtained.

[0052] Comparative Example 2

[0053] A method for preparing an alkyl organic phosphine antistatic agent comprises the following steps:

[0054] (1) 0.1 mol of 1-bromooctane and 0.1 mol of triethyl phosphite were mixed in equal molar ratios, added to a three-necked flask, and reacted at 180°C with magnetic stirring for 3 h for esterification reaction.

[0055] (2) After the reaction, the temperature was lowered to 120° C. and distilled under reduced pressure for 8 h to separate 1-bromoethane, unreacted 1-bromooctane, and triethyl phosphite, thereby obtaining 0.176 mol of the intermediate product, diethyl octylphosphonate.

[0056] (3) 0.1 mol of diethyl octylphosphonate was added to a three-necked flask, and 20.57 g of a 30% KOH aqueous solution was added dropwise under magnetic stirring at 120° C., and then the ester was hydrolyzed at 120° C. for 6 h. After the reaction was completed, the organic phosphine antistatic agent potassium monoethyl octylphosphonate was obtained.

[0057] Test Case

[0058] (1) Infrared spectrum test

[0059] The intermediate product diethyl octylphosphonate (a) and the product organic phosphine antistatic agent potassium monoethyl octylphosphonate (b) obtained in Example 1 of the present invention were detected by Fourier transform infrared spectrometer. The results are as follows: Figure 1 As shown. Figure 1 It can be seen that in the two spectral lines, 2840-2960cm -1 The stretching vibration peaks of CH2 and CH3 are at 1350-1470cm -1 The peaks are the bending vibration peaks of CH2 and CH3. Figure 1 In spectral line a, 1245cm -1 The peak of P=O stretching vibration is 1022cm -1 The peak is the stretching vibration peak of POC. Figure 1 Spectral line b, 3000-3600cm -1 The stretching vibration peak of OH is at 1170 cm -1 The peak of P=O stretching vibration is 1043 cm -1 The peak at 1646cm is the POC stretching vibration peak.-1 The peak at 37° is the O=P-OH stretching vibration peak, which proves that potassium monoethyl octylphosphonate has been synthesized.

[0060] (2) Mass spectrometry test

[0061] The product of the organic phosphine antistatic agent potassium monoethyl octylphosphonate obtained in Example 1 of the present invention was detected by mass spectrometry. The results were as follows: Figure 1 As shown. Figure 2 The results show that M is potassium monoethyl octylphosphonate (260.35 g / mol); m / z = 261 is [M+1H + ] mass spectrum peak; m / z=223 is the fragment structure [M-1K - ]; m / z=195 is a fragment structure [M-1K - -1C2H4]; the mass spectrum peak at m / z = 251 is the intermediate diethyl octylphosphonate, proving the synthesis of potassium monoethyl octylphosphonate.

[0062] (3) Antistatic performance test

[0063] GB / T 14342-2015 "Test Method for Specific Electrical Resistivity of Chemical Staple Fibers" was used to select ES fibers. The fiber specific electrical resistivity of old blank ES fibers, cleaned and unoiled ES fibers, and ES fibers treated with the organic phosphine antistatic agent of each embodiment / comparative example was tested. The ES fibers were then equilibrated under specific temperature and humidity conditions for 24 hours. The changes in fiber specific electrical resistivity before and after oiling were compared to determine whether the products had antistatic properties. The test results are shown in Table 1.

[0064] Table 1 Antistatic performance test results

[0065]

[0066] From the results in Table 1, it can be seen that the product potassium monoethyl octylphosphonate obtained in the examples of the present invention and the comparative example can effectively reduce the specific resistance of ES fiber. The specific resistance of ES fiber can be reduced from 10 13 The order of magnitude is reduced to 10 7 The order of magnitude proves that the product has good antistatic properties. Compared with the potassium monoethyl octylphosphonate prepared in Comparative Example 1, the embodiment of the present invention is significantly better in reducing the specific resistance of ES fiber, so the product synthesized by the solvent-free method has better performance.

[0067] The above description is merely a preferred embodiment of the present invention, and the present invention is not limited to the above embodiment. It is understood that other improvements and variations directly derived or imagined by those skilled in the art without departing from the spirit and concept of the present invention should be considered to be included in the scope of protection of the present invention.

Claims

1. A method for preparing an alkyl organic phosphine antistatic agent, characterized in that: The alkyl organic phosphine antistatic agent is potassium octylphosphonate monoethyl ester; the chemical structural formula of potassium octylphosphonate monoethyl ester is as follows: The preparation method comprises the following steps: (1) 1-bromooctane and triethyl phosphite are mixed in equal molar ratios, transported to a microreactor at a constant flow rate using a horizontal flow pump, and reacted under an oil bath; (2) After the reaction is completed, 1-bromoethane, unreacted 1-bromooctane and triethyl phosphite are distilled off under reduced pressure to obtain the intermediate product diethyl octylphosphonate; (3) adding the intermediate product and a KOH aqueous solution into a reaction vessel to carry out an ester hydrolysis reaction, and after the reaction is completed, obtaining the alkyl organic phosphine antistatic agent.

2. The preparation method according to claim 1, characterized in that In step (1), the microreactor is a microreactor processed into a coil style by a stainless steel capillary with an inner diameter of 2 mm and an outer diameter of 3 mm; the effective length of the microreactor is 5 m, and the effective length is the length of the stainless steel capillary part immersed in the oil bath.

3. The preparation method according to claim 1, characterized in that In step (1), the flow rate is 65-130 μL / min; the reaction temperature in the oil bath is 170-190° C., and the reaction time is 2-4 h.

4. The preparation method according to claim 1, characterized in that In step (2), the temperature of the reduced pressure distillation is 100-140° C., and the time is 6-12 h.

5. The preparation method according to claim 1, characterized in that In step (3), the mass concentration of KOH in the KOH aqueous solution is 20-30%; and the molar ratio of the intermediate product to KOH is 1:1-1.

3.

6. The preparation method according to claim 1, characterized in that In step (3), the temperature of the ester hydrolysis reaction is 115-130° C., and the time is 4-8 hours.

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