Preparation method of high-temperature-resistant phosphorus salt antistatic agent

Abstract

The invention discloses a preparation method of a high-temperature-resistant phosphorus salt antistatic agent, which comprises the following steps: by taking a bis (trifluoromethylsulfonyl) imine compound as shown in a chemical structural general formula (I) and a tetra-substituted phosphorus salt compound as shown in a formula (II) as raw materials, reacting in a mixed solvent of water and an organic solvent at room temperature to 100 DEG C for 5-20 hours; the structural general formula of the phosphorus salt antistatic agent is shown as (III). Experimental results show that the phosphorus salt antistatic agent prepared by the invention has excellent antistatic performance and long-time stability at high temperature. The preparation method disclosed by the invention has the characteristics of mild reaction conditions, few synthesis steps, simplicity and safety in operation and high yield, the raw materials used in the preparation process are all raw materials with simple synthesis process and high conversion rate, and the used substrate is wide in application range, low in cost and green and environment-friendly. Therefore, the method has a wide application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of antistatic agent synthesis, and particularly relates to a method for preparing a high temperature resistant phosphate antistatic agent. Background Art

[0002] Antistatic agent is a general term for chemicals that can guide or eliminate accumulated harmful charges so that they do not cause inconvenience or harm to production and life. There are four main types of traditional antistatic agents: one is small molecule inorganic salt antistatic agents, such as lithium trifluoromethanesulfonyl imide, which has the problem of unstable antistatic effect; the second is metal particles, which will increase the weight of the material and affect the material performance; the third is conductive carbon black, which has a good antistatic effect, but it will affect the material performance, and the color limitation also limits its use; the fourth is polymer antistatic agents, such as polyether type, sulfonic acid type, quaternary ammonium salt type, and polymer antistatic agents formed by acid functional groups grafted onto polymers.

[0003] Moreover, the above antistatic agents have the problem of unsatisfactory high temperature resistance and inability to maintain stable antistatic performance at high temperature for a long time, and are not suitable for use of plastics at high temperature. Therefore, it is urgent to design and synthesize a high temperature resistant phosphite antistatic agent. Summary of the invention

[0004] In view of the above problems existing in the prior art, the purpose of the present invention is to provide a method for preparing a high temperature resistant phosphate antistatic agent.

[0005] In order to achieve the above object, the present invention adopts the following technical solution:

[0006] The first aspect of the present invention provides a method for preparing a high temperature resistant phosphate antistatic agent, comprising the following steps:

[0007] Using a bistrifluoromethylsulfonyl imide compound of the general chemical structure shown in formula (I) and a tetrasubstituted phosphonium salt compound of the general chemical structure shown in formula (II) as raw materials, a reaction is carried out in a solvent to obtain a phosphonium salt antistatic agent of the general chemical structure shown in formula (III):

[0008]

[0009] Wherein, M includes but is not limited to H, Li, Na, Zn, and other metals that can form phosphite salts; R is selected from any one of C2-C6 alkyl and aryl groups, for example, ethyl, propyl, butyl, phenyl, etc.; R 1 Any one selected from C1-C6 alkyl and aryl, for example, methyl, ethyl, propyl, butyl, phenyl, etc.; X is selected from halogen, for example, fluorine, chlorine, bromine, etc.

[0010] Preferably, the reaction temperature is room temperature to 100° C., and the reaction time is 5 to 20 hours.

[0011] Preferably, the molar ratio of the bis(trifluoromethylsulfonyl)imide compound to the tetrasubstituted phosphonium salt compound is 0.5-1.5:1.0.

[0012] Preferably, the bis(trifluoromethylsulfonyl)imide compound is selected from:

[0013] Bis(trifluoromethanesulfonyl)imide

[0014]

[0015] Lithium bis(trifluoromethanesulfonyl)imide

[0016]

[0017] Sodium bis(trifluoromethanesulfonimide)

[0018]

[0019] Zinc bis(trifluoromethanesulfonyl)imide

[0020]

[0021] Preferably, the tetrasubstituted phosphonium salt compound is selected from any one of tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, tetrabutyl phosphonium iodide, tetraphenyl phosphonium chloride, triphenylmethyl phosphonium bromide, triphenylethyl phosphonium bromide, triphenylpropyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylpentyl phosphonium bromide, triphenylhexyl phosphonium bromide and tetraphenyl phosphonium bromide.

[0022] Preferably, the solvent is a mixed solvent of water and an organic solvent, and the molar ratio of the organic solvent to water is 0.1 to 10:1.

[0023] Preferably, the organic solvent is any one of tetrahydrofuran, methanol, acetonitrile, toluene, N,N-dimethylformamide, ethyl acetate, acetone, trifluoroethanol, dichloromethane, 1,2-dichloroethane, and 1-4-dioxane.

[0024] The second aspect of the present invention provides a high temperature resistant phosphate antistatic agent obtained by the above preparation method.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The present invention uses bis(trifluoromethylsulfonylimide) compounds and tetrasubstituted phosphonium salt compounds as raw materials, and adopts a one-step method to prepare a high temperature resistant phosphonium salt antistatic agent. Among them, the bis(trifluoromethylsulfonylimide) compounds and tetrasubstituted phosphonium salt compounds used as raw materials are raw materials with simple synthesis process and high conversion rate. The substrate used has a wide range of applications and has the characteristics of low cost and green environmental protection. The experimental results show that the phosphonium salt antistatic agent prepared by the present invention has excellent antistatic performance and long-term stability at high temperature.

[0027] (2) The preparation method of the present invention has the characteristics of simple and safe operation steps and high yield, and thus has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 A synthetic route for a high temperature resistant phosphite antistatic agent provided by the present invention;

[0030] Figure 2 is the NMR spectrum of the phosphite antistatic agent a prepared in Example 1;

[0031] Figure 3 is the carbon spectrum of the phosphite antistatic agent a prepared in Example 1;

[0032] Figure 4 is the fluorine spectrum of the phosphite antistatic agent a prepared in Example 1;

[0033] Figure 5 The results of high temperature thermal stability tests are as follows: (a) the phosphite antistatic agent a prepared in Example 1; (b) the ammonium salt ionic liquid. DETAILED DESCRIPTION

[0034] In the following description, for the purpose of illustration rather than limitation, specific details such as specific system structures and technologies are provided to provide a thorough understanding of the embodiments of the present invention. However, it should be clear to those skilled in the art that the present invention may also be implemented in other embodiments without these specific details.

[0035] Example 1

[0036] Reference Figure 1, which is a synthetic route of the phosphonium salt antistatic agent provided by the present invention, specifically preparing a bis(trifluoromethylsulfonyl)imide tetrabutyl phosphonium salt compound having a structural formula as shown in formula (a), recorded as phosphonium salt antistatic agent a.

[0037]

[0038] Add bis(trifluoromethylsulfonyl)imide (28.1 g, 0.1 mol, 1.0 equiv) and tetrabutylphosphonium bromide (37.3 g, 0.11 mol, 1.1 equiv) to a reaction flask, add to a mixed solvent of water (200 mL) and dichloromethane (200 mL), react at room temperature for 10 h, separate and evaporate the solvent to obtain a white solid (51.7 g, 96%), i.e., phosphite antistatic agent a. Its NMR, carbon spectrum, and fluorine spectrum results are as follows: Figure 2-4 shown.

[0039] 1 H NMR (400MHz) δ2.19-1.98 (m, 8H), 1.51 (d, J = 3.5Hz, 16H), 0.97 (t, J = 6.5Hz, 12H). 13 CNMR(101MHz)δ119.89(q,J=322.19Hz),121.49(s),118.29(s),115.10(s),23.77(d,J=15.3Hz),23.44(d,J=4.7Hz),18.68,18.21,13.24. 19 F NMR (367 MHz) 78.85.

[0040] Example 2

[0041] Add bistrifluoromethylsulfonyl imide (28.1 g, 0.1 mol, 1.0 equiv) and tetrabutylphosphonium chloride (59 g, 0.2 mol, 2.0 equiv) to a reaction flask, add to a mixed solvent of water (200 mL) and acetonitrile (200 mL), react at 80 ° C for 10 h, separate and evaporate the solvent to obtain a white solid (53.3 g, 99%), i.e., phosphine salt antistatic agent a.

[0042] Example 3

[0043] Add bis(trifluoromethylsulfonyl) lithium (28.7 g, 0.1 mol, 1.0 equiv) and tetrabutylphosphine chloride (59 g, 0.2 mol, 2.0 equiv) into a reaction flask, add to a mixed solvent of water (200 mL) and dichloroethane (200 mL), react at room temperature for 20 h, separate and evaporate the solvent to obtain a white solid (53.3 g, 99%), i.e., phosphine salt antistatic agent a.

[0044] Example 4

[0045] Zinc bis(trifluoromethylsulfonyl imide) (62.3 g, 0.1 mol, 1.0 equiv) and tetrabutylphosphonium chloride (59 g, 0.2 mol, 2.0 equiv) were added to a reaction flask, added to a mixed solvent of water (200 mL) and ethyl acetate (200 mL), reacted at 80 ° C for 5 h, separated and evaporated to obtain a white solid (46.5 g, 86%), i.e., phosphonium salt antistatic agent a.

[0046] Example 5

[0047] Add bis(trifluoromethylsulfonyl)lithium (28.7 g, 0.1 mol, 1.0 equiv) and tetraphenylphosphonium bromide (41.9 g, 0.1 mol, 1.0 equiv) into a reaction flask, add to a mixed solvent of water (200 mL) and dichloromethane (200 mL), react at room temperature for 10 h, separate and evaporate the solvent to obtain a white solid (56.3 g, 91%), i.e., phosphonium salt antistatic agent a.

[0048] Example 6

[0049]

[0050] To a reaction flask, add bis(trifluoroalkylsulfonyl)imide (28.1 g, 0.1 mol, 1.0 equiv) and tetraphenylphosphonium bromide (41.9 g, 0.1 mol, 1.0 equiv) and a mixed solvent of water (200 mL) and dichloroethane (200 mL), react at 50° C. for 15 h, separate the liquids and evaporate the solvent to obtain a white solid (55.1 g, 89%), i.e., a bis(trifluoromethylsulfonyl)imide tetraphenylphosphonium salt compound having a structural formula as shown in formula (b), recorded as phosphonium salt antistatic agent b. 1 H NMR (CDCl 3 )δppm:8.01(m,4H),7.99(m,8H),7.77(m,8H); 13 C NMR (CDCl 3 )δppm:121.60,131.7(d,J=17Hz),135.98,136.77,142.53. 19 F NMR (CDCl 3 )δppm:-78.72

[0051] Example 7

[0052]

[0053] Add bis(trifluoromethylsulfonyl)lithium (28.7 g, 0.1 mol, 1.0 equiv) and methyltriphenylphosphonium bromide (42.8 g, 0.12 mol, 1.2 equiv) into a reaction flask, add into a mixed solvent of water (200 mL) and dichloroethane (200 mL), react at 60° C. for 10 h, separate and evaporate the solvent to obtain a white solid (54.0 g, 97%), i.e., a bis(trifluoromethylsulfonyl)imidemethyltriphenylphosphonium salt compound having a structural formula as shown in formula (c), recorded as phosphonium salt antistatic agent c. 1 H NMR (CDCl 3 )δ7.85-7.81(m,3H),7.72-7.71(m,6H),7.70-7.59(m,6H),2.82(d,J=13.2Hz,3H); 13 C NMR (CDCl 3 )δ135.38,135.36,132.97,132.89,130.61,130.51,121.10,119.03,118.32,9.72,9.25; 19 FNMR (CDCl 3 ):δ-79.48

[0054] Example 8

[0055]

[0056] Lithium bis(trifluoromethylsulfonyl)imide (28.7 g, 0.1 mol, 1.0 equiv) and triphenylbutylphosphonium bromide (55.6 g, 0.15 mol, 1.5 equiv) were added to a reaction flask, added to a mixed solvent of water (200 mL) and dichloromethane (200 mL), reacted at room temperature for 15 h, separated and the solvent was evaporated to obtain a white solid (53.1 g, 93%), i.e., a bis(trifluoromethylsulfonyl)imide triphenylbutylphosphonium salt compound having a structural formula as shown in formula (d), recorded as phosphonium salt antistatic agent d. 1 H NMR (400 MHz; CDCl 3 )δ7.83-7.62(m,15H),3.12(d,J=14.2Hz,2H),1.60(d,J=28.0Hz,4H),0.92(d,J=6.4Hz,3H). 13 C NMR (101 MHz; CDCl 3 )δ135.4,133.3,130.7,124.8-115.2,118.4-117.5,24.4,23.7,22.2,13.4. 19 F NMR (376 MHz; CDCl 3)δ-78.6.

[0057] The antistatic performance of the target products obtained in Examples 1-8 was tested, and the results are shown in Table 1.

[0058] Compound resistance Phosphate antistatic agent <![CDATA[1.8*10 4 ]]> Phosphate antistatic agent b <![CDATA[2.6*10 4 ]]> Phosphate antistatic agent c <![CDATA[2.9*10 4 ]]> Phosphate antistatic agent <![CDATA[4.3*10 4 ]]>

[0059] It can be seen from the results in Table 1 that the phosphite antistatic agent ad prepared in the present invention has excellent antistatic performance at high temperatures.

[0060] The phosphite antistatic agent a prepared in Example 1 was tested for high temperature thermal stability. Figure 5 .

[0061] Depend on Figure 5 The results show that under the heating condition of 300°C for 24 hours, the phosphite antistatic agent a did not change color, while the ammonium salt ionic liquid changed color due to oxidation. This indicates that the phosphite antistatic agent prepared by the present invention has excellent long-term stability at high temperature.

[0062] The present invention is not limited to the above-mentioned specific implementation modes. Various changes made by ordinary technicians in this field based on the above-mentioned concepts without creative work are all within the protection scope of the present invention.

Claims

1. A method for preparing a high temperature resistant phosphate antistatic agent, characterized in that: The method comprises the following steps: using a bistrifluoromethylsulfonyl imide compound having a chemical structure shown in formula (I) and a tetrasubstituted phosphonium salt compound having a chemical structure shown in formula (II) as raw materials, reacting in a solvent to obtain a phosphonium salt antistatic agent having a chemical structure shown in formula (III): Wherein, M is selected from any one of H, Li, Na, and Zn, R is selected from any one of C2-C6 alkyl and aryl, and R 1 is selected from any one of C1-C6 alkyl and aryl, and X is selected from halogen.

2. The method for preparing the high temperature resistant phosphate antistatic agent according to claim 1, characterized in that: The reaction temperature is room temperature to 100° C., and the reaction time is 5 to 20 hours.

3. The method for preparing the high temperature resistant phosphate antistatic agent according to claim 1, characterized in that: The molar ratio of the bis(trifluoromethylsulfonyl)imide compound to the tetrasubstituted phosphonium salt compound is 0.5-1.5:1.

0.

4. The method for preparing the high temperature resistant phosphate antistatic agent according to claim 1, characterized in that: The bis(trifluoromethylsulfonylimide) compound is selected from any one of bis(trifluoromethylsulfonylimide), bis(trifluoromethylsulfonylimide) lithium, bis(trifluoromethylsulfonylimide) sodium and bis(trifluoromethylsulfonylimide) zinc.

5. The method for preparing the high temperature resistant phosphate antistatic agent according to claim 1, characterized in that: The tetrasubstituted phosphonium salt compound is selected from any one of tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, tetrabutyl phosphonium iodide, tetraphenyl phosphonium chloride, triphenylmethyl phosphonium bromide, triphenylethyl phosphonium bromide, triphenylpropyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylpentyl phosphonium bromide, triphenylhexyl phosphonium bromide and tetraphenyl phosphonium bromide.

6. The method for preparing the high temperature resistant phosphate antistatic agent according to claim 1, characterized in that: The solvent is a mixed solvent of water and an organic solvent, and the molar ratio of the organic solvent to water is 0.1 to 10:

1.

7. The method for preparing the high temperature resistant phosphate antistatic agent according to claim 6, characterized in that: The organic solvent is any one of tetrahydrofuran, ethanol, methanol, acetonitrile, toluene, N,N-dimethylformamide, dimethyl sulfoxide, ethyl acetate, acetone, trifluoroethanol, dichloromethane, 1,2-dichloroethane, and 1-4-dioxane.

8. A high temperature resistant phosphate antistatic agent obtained by the preparation method according to any one of claims 1 to 7.

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