CN101456830B - Methods of making an antistatic agent - Google Patents

Abstract

(R)₄P-Z (3)。A method for preparing phosphonium sulfonate salts of general formula (1): wherein each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than about 0.90; p is 0 or 1, and q and r are 0 to about An integer of 7, provided that q+r is less than 8, and if p is not 0, then r is greater than 0; each R is the same or different hydrocarbyl group containing 1 to about 18 carbon atoms, the method comprising using in an aqueous medium A compound of general formula (2): wherein M is Li or Na, X, q, p and r are as defined above, mixed with a stoichiometric excess of a compound of general formula (3): wherein Z is a halogen, R is as defined above; and from the The medium separates the product of formula (1).

(R) ₄ PZ (3).

Description

A kind of preparation method of antistatic agent

This application is a divisional application with the filing date of April 7, 2005, the application number of 200580012095.8 (PCT/US2005/011756), and the title of "A Preparation Method of Antistatic Agent".

Cross References to Related Applications

This application claims priority to US Provisional Application Serial No. 60/562,010, filed April 13, 2004, which is hereby incorporated by reference in its entirety.

Background of the invention

The present disclosure relates to a method of preparing an antistatic agent.

Thermoplastics are used to make a wide variety of objects and components from automotive parts to electronic appliances. Because of their widespread use especially in electrical appliances, it is desirable to provide thermoplastic resins containing antistatic agents. Many polymers or blends of polymers are relatively insulating, which can lead to a buildup of static charge during handling and use of the polymers. For example, charged moldings can attract small dust particles, which can affect the appearance of smooth surfaces, for example by making the item less transparent. In addition, electrostatic charges can be a serious obstacle in the preparation of such polymers.

Antistatic agents are materials that are added to polymers to reduce their tendency to acquire a static charge, or, when a charge is present, to facilitate the dissipation of such charge. Organic antistatic agents are either hydrophilic or ionic in nature. When present on the surface of polymeric materials, they facilitate electron transfer, thereby eliminating static charge buildup. The antistatic agent has been added to the polymer composition before further processing into an article and is thus referred to as "internal applied". Useful antistatic agents applied in this manner are thermally stable and migrate to the surface during processing.

A large number of antistatic agents having surfactants as their main components have been considered and tested. Many suffer from one or more deficiencies such as incompatibility with the polymer (which affects uniform dispersion), poor thermal stability and/or poor antistatic properties. In particular, poor heat resistance can adversely affect the optical properties of engineering thermoplastics such as aromatic polycarbonates.

However, certain phosphonium salts of certain sulfonic acids have been shown to be useful antistatic agents. U.S. Patent No. 4,943,380 discloses reducing the charge on polycarbonate resins with an antistatic composition containing 90-99.9% by weight of polycarbonate and 0.1-10% by weight of a heat-resistant phosphonium sulfonate of the general formula:

Wherein R is a straight chain or branched chain alkyl group with 1-18 carbon atoms; R ₁ , R ₂ and R ₃ are the same, and each is an aliphatic hydrocarbon group with 1-8 carbon atoms or an aliphatic group with 6-12 carbon atoms Aromatic hydrocarbon group; and R ₄ is a hydrocarbon group with 1-18 carbon atoms.

US Patent No. 6,194,497 discloses antistatic resin compositions, particularly transparent resin compositions, comprising a thermoplastic composition and a halogenated medium or short chain alkylsulfonate of a tetrasubstituted phosphonium cation. The antistatic agents described therein are prepared by ion exchange of potassium haloalkylsulfonates to generate the corresponding acids. The haloalkylsulfonic acid reacts with tetrabutylphosphonium hydroxide to generate the antistatic agent.

One advantage of this synthesis is that the use of an ion exchange step during the synthesis results in a product that is very pure, ie, contains little to no halogenated compounds that would eventually degrade the resin, such as polycarbonate. Although suitable for its intended purpose, this particular synthesis has a number of disadvantages. For example, employing an ion exchange step increases processing costs and may result in the generation of waste requiring disposal procedures. The synthesis also uses potassium salts as starting products, which are prepared from the corresponding sulfonyl fluorides. Because the solubility of potassium peralkylsulfonate is relatively low, eg, about 5% at 20°C, a water/ethanol mixture is required for ion exchange. The flammability of ethanol requires that effective safety precautions be implemented in the synthesis. In addition, it is also important to choose an appropriate water/ethanol ratio. Excess ethanol will dissolve the final product in the reaction solvent so that further extraction steps may be required to isolate the product.

Therefore, there is still a need in the art for more efficient methods, especially one-step methods, to prepare phosphonium sulfonate antistatic agents and thermoplastic resin compositions incorporating these antistatic agents. It is also desirable that such processes produce antistatic agents in good yields without adversely affecting the safety of the process and/or the purity of the product.

Brief description of the invention

The process for preparing phosphonium sulfonate salts of formula (1) addresses the above and other deficiencies in the art:

wherein each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than about 0.90; p is 0 or 1, and q and r are integers from 0 to about 7, provided that q+r is less than 8 and if p is not 0 , then r is greater than 0; each R is independently a hydrocarbon group with 1 to about 18 carbon atoms, and the method comprises making the formula (2) compound in an aqueous medium:

Wherein M is Li or Na, X, q, p and r are as defined above, mixed with the compound of formula (3):

(R) ₄ PZ (3)

wherein Z is a halogen, and R is as defined above; then the product of formula (1) is separated from the aqueous medium.

In another embodiment, the method for preparing the phosphonium sulfonate salt of formula (1) comprises first in an aqueous medium, making the compound of formula (4):

Mixed with a stoichiometric excess of a compound of general formula (5):

(R) ₄ P-OH (5)

Wherein X, p, q, r and R have the same meanings as in formula (1); and then separate the product of formula (1) from the aqueous medium.

In another embodiment, the method for preparing the phosphonium sulfonate salt of formula (1) comprises making sodium hydroxide and/or lithium hydroxide and the compound of above-mentioned general formula (4) and the compound of above-mentioned general formula (3) in water mixing in a medium, wherein X, q, p, r and R are as defined above; and separating the phosphonium sulfonate of formula (1) from said aqueous medium.

Another embodiment includes antistatic agents of formula (1) prepared by one of the aforementioned methods.

In yet another embodiment, there is provided a thermoplastic composition comprising a thermoplastic polymer and an antistatic agent prepared by one of the aforementioned methods.

The present invention includes:

1. a method for preparing the phosphonium sulfonate salt of general formula (1):

wherein each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than about 0.90; p is 0 or 1, and q and r are integers from 0 to about 7, provided that q+r is less than 8, and if p is not 0, then r is greater than 0; each R is the same or different hydrocarbyl containing 1 to about 18 carbon atoms, the method comprising:

Make the compound of general formula (2) in aqueous medium:

wherein M is Li or Na, X, q, p and r are as defined above, mixed with a stoichiometric excess of the compound of general formula (3):

(R) ₄ PZ (3)

wherein Z is halogen and R is as defined above; and

The phosphonium sulfonate of formula (1) is isolated from the aqueous medium.

2. The method of item 1, wherein X is fluorine; Z is bromine or chlorine; the three R groups can be the same aliphatic hydrocarbon group containing 1 to about 8 carbon atoms or an aromatic hydrocarbon containing 6 to about 12 carbon atoms group, the fourth R group is a hydrocarbyl group containing 1 to about 18 carbon atoms.

3. The method of item 2, wherein p is 0.

4. The method of item 1, wherein the sulfonate is perfluoromethanesulfonate, perfluoroethanesulfonate, perfluoropropanesulfonate, perfluorobutanesulfonate, perfluoropentanesulfonate, perfluorohexylsulfonate, fluoroheptyl sulfonate, perfluorooctyl sulfonate, or a combination containing at least one of the foregoing sulfonates; and wherein the phosphonium is tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, Tributylmethylphosphonium, Tributylethylphosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphosphonium, Trimethyldodecylphosphonium, Trimethylstearylphosphonium, Triethyloctylphosphonium and aromatic phosphonium such as tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium, or a combination comprising at least one of the foregoing phosphoniums.

5. The method of item 4, wherein the sulfonate is perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexylsulfonate, perfluoroheptylsulfonate, perfluorooctylsulfonate or an anion comprising at least one of the aforementioned organic sulfonate combination, the phosphonium is tetrabutylphosphonium.

6. The method of item 1, wherein the molar ratio of the compound of formula (2) to the compound of formula (3) is about 1:1.001 to about 1:1.5.

7. The method of item 1, wherein the molar ratio of the compound of formula (2) to the compound of formula (3) is about 1.001:1 to about 1.5:1.

8. The method of item 1, wherein the aqueous medium comprises less than about 1 volume percent of the non-aqueous medium.

9. The method of item 1, wherein the phosphonium sulfonate product is precipitated from said aqueous medium.

10. A method for preparing a phosphonium sulfonate salt of general formula (1):

wherein each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than about 0.90; p is 0 or 1, q and r are integers from 0 to about 7, provided that q+r is less than 8, and if p is not is 0, then r is greater than 0; each R is the same or different hydrocarbon groups containing 1 to about 18 carbon atoms, and the method includes:

In aqueous medium, make the compound of general formula (4)

Wherein the meaning of X, p, q and r is the same as in formula (1), mixed with the compound of general formula (5):

(R) ₄ P-OH (5)

wherein R has the same meaning as in formula (1); and

Isolate the phosphonium sulfonate product of formula (1).

11. The method of item 10, wherein X is fluorine; Z is bromine or chlorine; the three R groups are the same aliphatic hydrocarbon group containing 1 to about 8 carbon atoms or an aromatic hydrocarbon group containing 6 to about 12 carbon atoms, the The four R groups are hydrocarbyl groups containing 1 to about 18 carbon atoms.

12. The method of item 11, wherein p is 0.

13. The method of item 10, wherein the sulfonate is perfluoromethanesulfonate, perfluoroethanesulfonate, perfluoropropanesulfonate, perfluorobutanesulfonate, perfluoropentanesulfonate, perfluorohexylsulfonate, perfluoro Heptylsulfonate, perfluorooctylsulfonate, or a combination containing at least one of the foregoing sulfonates; wherein the phosphonium is tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium Phosphonium, Tributylethylphosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphosphonium, Trimethyldodecylphosphonium, Trimethylstearylphosphonium, Triethylphosphonium Octylphosphonium and aromatic phosphonium such as tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium or a combination comprising at least one of the foregoing phosphoniums.

14. The method of item 13, wherein the sulfonate is perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexylsulfonate, perfluoroheptanesulfonate, perfluorooctylsulfonate or comprises at least one of the aforementioned organic sulfonate A combination of anions, the phosphonium being tetrabutylphosphonium.

15. The method of item 14, wherein the molar ratio of the compound of formula (4) to the compound of formula (3) is about 1:2.01 to about 1:3.

16. The method of item 10, wherein the aqueous medium comprises less than about 1 volume percent of the non-aqueous medium.

17. The method of item 10, wherein the phosphonium sulfonate product is precipitated from the aqueous medium.

18. A method for preparing a phosphonium sulfonate salt of general formula (1):

wherein each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than about 0.90; p is 0 or 1, q and r are integers from 0 to about 7, provided that q+r is less than 8, and if p is not is 0, then r is greater than 0; each R is the same or different hydrocarbon groups containing 1 to about 18 carbon atoms, and the method includes:

In an aqueous medium, sodium hydroxide and/or lithium hydroxide;

Compounds of general formula (4)

Wherein X, p, q and r have the same meaning as in formula (1); and

Compounds of general formula (3) are mixed:

(R) ₄ PZ (3)

wherein Z is halogen and R is as defined above; and

The phosphonium sulfonate of formula (1) is isolated.

19. The method of item 18, wherein the molar ratio of the compound of formula (4) to the compound of formula (3) is about 1:2.01 to about 1:3.

20. The method of item 18, wherein X is fluorine; Z is bromine or chlorine; the three R groups are identical aliphatic hydrocarbon groups containing 1 to about 8 carbon atoms or aromatic hydrocarbon groups containing 6 to about 12 carbon atoms, The fourth R group is a hydrocarbyl group containing 1 to about 18 carbon atoms.

21. The method of item 18, wherein p is 0.

22. The method of item 18, wherein the sulfonate is perfluoromethanesulfonate, perfluoroethanesulfonate, perfluoropropanesulfonate, perfluorobutanesulfonate, perfluoropentanesulfonate, perfluorohexylsulfonate, perfluoroheptylsulfonate Sulfonate, perfluorooctylsulfonate, or a combination containing at least one of the foregoing sulfonates; wherein the phosphonium is tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium Phosphonium, Tributylethylphosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphosphonium, Trimethyldodecylphosphonium, Trimethylstearylphosphonium, Triethylphosphonium Octylphosphonium and aromatic phosphonium such as tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium or a combination comprising at least one of the foregoing phosphoniums.

23. The method of item 22, wherein the sulfonate is perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexylsulfonate, perfluoroheptanesulfonate, perfluorooctylsulfonate or an anion comprising at least one of the foregoing organic sulfonate combination, the phosphonium is tetrabutylphosphonium.

24. The method of item 18, wherein the aqueous medium comprises less than about 1 volume percent of the non-aqueous medium.

25. The method of item 18, wherein the phosphonium sulfonate product is precipitated from said aqueous medium.

26. The method of item 18, wherein lithium hydroxide and/or sodium hydroxide is added to the compound of formula (4) prior to the compound of formula (5).

27. The method of item 26, wherein the product after adding lithium hydroxide and/or sodium hydroxide is the corresponding basic sulfonate (2).

28. The method of item 25, further comprising isolating salt (2) before adding the compound of formula (5).

Detailed description of the invention

The present inventors have surprisingly found that haloalkylsulfonic acids suitable for use as antistatic agents can be easily obtained in one step in aqueous medium from the corresponding tetraalkylphosphonium halides and haloalkylsulfonate lithium or sodium salts Phosphonium salt. Alternatively, the haloalkylphosphonium sulfonate salt can be obtained in one step in aqueous medium from the corresponding tetraalkylphosphonium halide or hydroxide and haloalkylsulfonyl fluoride. The reactants were readily available, and the use of water as the reaction solvent accelerated the separation of the products. Thus, by virtue of a surprisingly beneficial feature, the inventors have discovered that simple mixing of the reactants leads to precipitation of the targeted antistatic molecule in high yields.

In general, the phosphonium haloalkylsulfonate has the general formula (1):

wherein X is independently selected from halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than about 0.90. Halogen may be independently selected from bromine, chlorine, fluorine and iodine. In particular, halogen is fluorine.

Furthermore, in formula (1), p is 0 or 1, q and r are integers from 0 to about 7, provided that q+r is less than 8, and if p is not 0, then r is greater than 0. In one embodiment, p is zero.

Each R in the formula (1) is independently a hydrocarbon group containing 1 to about 18 carbon atoms, that is, each R is the same or different, and can be a straight chain or branched aliphatic hydrocarbon group containing 1 to about 18 carbon atoms, or contains An aromatic hydrocarbon group of 6 to about 18 carbon atoms. "Aromatic" groups as used herein include peraryl groups, aralkyl groups and alkylaryl groups. In one embodiment, the three R groups in the organophosphonium cation can be the same aliphatic group containing 1 to about 8 carbon atoms or an aromatic group containing 6 to about 12 carbon atoms, while the fourth R group The group can be a hydrocarbyl group containing from 1 to about 18 carbon atoms.

Thus, the antistatic agent may be a highly halogenated phosphonium sulfonate salt containing an organic sulfonate anion and a tetrasubstituted organophosphonium cation. Specific examples are perfluorinated salts, but due to the method of preparation of fluorination (electrolysis), sometimes only partially fluorinated compounds are produced.

Specific examples of suitable organic sulfonate anions include: perfluoromethanesulfonate, perfluoroethanesulfonate, perfluoropropanesulfonate, perfluorobutanesulfonate, perfluoropentanesulfonate, perfluorohexylsulfonate, perfluoroheptylsulfonate Sulfonate and PFOS. There are also combinations of the foregoing.

Examples of specific phosphonium cations include cations such as tetramethylphosphonium, tetraethylphosphonium, tetra-n-propylphosphonium, tetraisopropylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, Tributylethylphosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphosphonium, Trimethyldodecylphosphonium, Trimethylstearylphosphonium, Triethyloctyl Phosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, and tributylbenzylphosphonium. There are also combinations of the above.

In one embodiment, there is provided a method for preparing a phosphonium sulfonate of formula (1), which comprises making the compound of formula (2) in an aqueous medium:

wherein M is an alkali metal selected from lithium (Li) or sodium (Na), and X, q, p and r are as defined above, mixed with a stoichiometric excess of the compound of formula (3):

(R) ₄ PZ (3)

Wherein Z is a halogen, and R is as defined above; the product of formula (1) is separated again. Z can specifically be bromine or chlorine.

In one embodiment, the method may comprise dissolving a sodium or lithium salt of perhaloalkylsulfonate of formula (2) in an aqueous medium. For example, the aqueous medium may be substantially free of co-solvents such as ethanol. "Aqueous medium" as used herein refers to a solution, dispersion or suspension in water. Furthermore, as used herein, an aqueous medium that is "substantially free of co-solvents" refers to an aqueous medium that contains less than about 1, especially less than about 0.5, and more particularly less than about 0.1 volume percent of a co-solvent. Although the use of co-solvents is possible and necessary in the case of potassium salts, the use of water substantially free of co-solvents results in higher purity products and avoids the safety concerns associated with the use of volatile solvents. When employed, suitable co-solvents to help dissolve the alkali metal sulfonate include lower alcohols such as methanol, acetic acid, etc. and chlorinated solvents such as dichloromethane, etc. Mixtures of co-solvents may be used.

The aqueous medium containing the alkali metal salt of perhaloalkylsulfonic acid can then be reacted with tetrasubstituted phosphonium halide. The order of addition does not appear to be critical, i.e., can also be achieved by, for example, dissolving a tetrasubstituted phosphonium halide in an aqueous medium and adding the alkali metal perhaloalkylsulfonate; by simultaneously dissolving and mixing the reactants; by dissolving and mixing separately The reactants and other methods complete the reaction. The phosphonium sulfonate salts obtained herein can be obtained by using a mixture of an alkali metal perhaloalkylsulfonate and a tetrasubstituted phosphonium halide.

The process can be carried out over a wide range of temperatures and reaction times and will depend on the particular reactants used, co-solvents (if any), desired yield, desired purity, cost, convenience, Factors such as ease of preparation are considered. For example, the temperature of the various methods may generally range from about 10°C to about 100°C, specifically from about 20°C to about 95°C, more specifically from about 30°C to about 90°C. In one embodiment, the reaction is carried out at room or ambient temperature, generally from about 20°C to about 25°C. Likewise, the reaction time can vary, but generally ranges from about 5 minutes to about 1 day, specifically from about 30 minutes to about 12 hours, or more specifically from about 60 minutes to about 4 hours. These temperatures and times can vary widely and can be determined by one of ordinary skill in the art.

The tetrasubstituted phosphonium halide can be used in at least an equimolar amount relative to the perhaloalkyl sulfonate, more particularly, the molar ratio of the perhaloalkyl sulfonate of formula (2) to the tetrasubstituted phosphonium halide of formula (3) can be about 1:1.001-about 1:1.5, especially about 1:1.002-about 1:1.1, more particularly about 1:1.005-about 1:1.015. Optimum ratios vary depending on the specific reactants, temperature, cosolvent (if any), and time, and are readily determined by one of ordinary skill in the art.

In another embodiment, the molar ratio of the perhaloalkylsulfonate of formula (2) to the tetrasubstituted phosphonium halide of formula (3) may be from about 1.001:1 to about 1.5:1, especially from about 1.002:1 to About 1.1:1, more particular amounts of about 1.005:1 to about 1.015:1. Optimum ratios vary depending on the specific reactants, temperature, cosolvent (if any), and time, and are readily determined by one of ordinary skill in the art.

According to a very advantageous feature, the reactants and the aqueous medium are chosen such that the phosphonium sulfonate salt (1) precipitates from the aqueous medium in high purity and can be freed from impurities, especially halogen-containing impurities, by simple filtration and washing separated. It is especially desirable to remove halogen-containing impurities (such as tetrasubstituted phosphonium bromides and/or tetrasubstituted phosphonium chlorides), since these impurities are known to degrade resins such as polycarbonates. Since the impurities are soluble in water but the desired product is insoluble in water, the impurities can be easily and effectively removed by washing with water.

In yet another embodiment, a kind of method for preparing formula (1) phosphonium sulfonate is provided, it comprises making the sulfonyl fluoride of general formula (4) in aqueous medium:

Wherein X, p, q and r are as above, combined with a tetrasubstituted phosphonium hydroxide of formula (5) in stoichiometric excess:

(R) ₄ P-OH (5)

wherein R is as defined above; and the product of formula (1) is separated from the aqueous medium. In one embodiment, the reactants and the aqueous medium are selected such that the phosphonium sulfonate salt is precipitated from the aqueous medium.

In this embodiment, phosphonium sulfonate salts of formula (1) can be prepared in a one-step process, which can include reacting sulfonyl fluoride (4) with tetrasubstituted phosphonium hydroxide (5) in an aqueous medium in a single vessel. Therefore, the compound (4) can be dispersed or dissolved in an aqueous medium containing a co-solvent or substantially free of a co-solvent as described above, and the tetrasubstituted phosphonium hydroxide (5) can be added thereto. The order of addition does not appear to be critical, i.e., can also be obtained by, for example, dissolving the tetrasubstituted phosphonium hydroxide (5) in an aqueous medium and adding the sulfonyl fluoride (4), or by simultaneously dissolving/dispersing and mixing the reaction The reaction is completed. Combinations of different sulfonyl fluorides (4) and/or different tetrasubstituted phosphonium hydroxides (5) can be reacted.

As noted above, a wide range of reaction times, temperatures and other process conditions can be employed, but room temperature is preferred for ease of preparation. Generally, tetrasubstituted phosphonium hydroxide (5) is used in an amount of at least about 2 moles per mole of sulfonyl fluoride (4). More particularly, the molar ratio of the compound of formula (4) to the phosphonium hydroxide of formula (5) can be about 1:2.01-about 1:3, especially about 1:2.1-about 1:2.7, more particularly about 1:2.2-about 1:2.6. Optimum ratios will vary depending on the specific reactants, temperature, co-solvent (if any), and time, and are readily determined by one of ordinary skill in the art.

In yet another embodiment, there is provided a method for preparing a phosphonium sulfonate salt of formula (1), which comprises, in an aqueous medium, making a sulfonyl fluoride of formula (4), a tetrasubstituted phosphonium halide of formula (3) and a base metal or alkaline earth metal base mixing; then separating the phosphonium sulfonate of formula (1) from said aqueous medium. Suitable bases include, for example, alkaline hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide, magnesium hydroxide, and the like. Mixtures may also be used. Preference is given to potassium hydroxide, sodium hydroxide and/or lithium hydroxide. In one embodiment, the reactants and the aqueous medium are selected so as to precipitate the phosphonium sulfonate salt from the aqueous medium.

Furthermore, the order of addition does not appear to be critical, therefore, the components can be mixed simultaneously, or the tetrasubstituted phosphonium (3) halide can be added to the aqueous solution/dispersion of the base and the medium/dispersion added to Solutions/Dispersions of Sulfonyl Fluoride (4). In yet another embodiment, the sulfonyl fluoride (4) and the base are mixed and reacted for a period of time effective to form the basic sulfonate salt (2). Then, without isolation of the basic sulfonate (2), the phosphonium halide (3) is added to the medium to form the product. The method is simple, efficient and minimizes time and materials. Alternatively, the basic sulfonate (2) can be isolated and redissolved with or without a cosolvent before adding the phosphonium halide (3). A wide range of reaction times, temperatures and other process conditions can be used, but about 25°C (room temperature) to about 100°C is preferred for ease of preparation. Optimum reactant ratios are readily determined by one of ordinary skill in the art and may be, for example, those described above.

Phosphonium sulfonate salts that can be prepared by the methods described herein include those having the general formula (6):

wherein F is fluorine; n is an integer from 0 to about 7, S is sulfur; each R is the same or different aliphatic hydrocarbon radicals containing 1 to about 18 carbon atoms or aromatic hydrocarbon radicals containing 6 to about 18 carbon atoms . In one embodiment, the three R groups in the organophosphonium cation can be the same aliphatic group containing 1 to about 8 carbon atoms or an aromatic group containing 6 to about 12 carbon atoms, while the fourth The R group can be a hydrocarbyl group containing 1 to about 18 carbon atoms. The antistatic composition containing the phosphonium fluoride sulfonate of formula (6) as its main component can be used in many different ways to take advantage of its antistatic properties, compatibility and heat resistance, for example, to provide thermoplastic resins with such Antistatic properties. Suitable thermoplastic resins include, but are not limited to, polycarbonates, polyetherimides, polyesters, polyphenylene ether/polystyrene blends, polyamides, polyketones, acrylonitrile-butadiene-styrene copolymers (ABS), or a mixture comprising at least one of the foregoing polymers. Phosphonium sulfonate salts are low-melting semi-solid materials, so they can be handled as molten liquids. Certain embodiments of the present disclosure are solid crystalline materials at room temperature (about 15 to about 25°C), which are easily weighed, handled, and added to the thermoplastic resins described above.

In addition to the thermoplastic resin, the thermoplastic composition may contain various additives that are generally incorporated into such resin compositions. Mixtures of additives may be used. Such additives may be incorporated at appropriate times during mixing of the components to form the composition. Examples of suitable additives are impact modifiers, fillers, heat stabilizers, antioxidants, light stabilizers, plasticizers, release agents, UV absorbers, lubricants, pigments, dyes, colorants, foaming agent, anti-dripping agent and flame retardant.

A common way of carrying out this process is to add the additive directly to the thermoplastic resin and allow it to mix as the polymer is formed or formed. This can be done by conventional means including extrusion, injection, molding, compression molding or casting. The thermoplastic composition can be prepared by methods commonly available in the art, for example, in one embodiment, in one embodiment, the thermoplastic resin, antistatic agent and/or other optional components are first pulverized, Mix in a Henschel high speed mixer, optionally with chopped glass strands or other fillers. Other low shear treatments including, but not limited to, hand stirring can also accomplish this mixing. The mixture is then fed into the inlet of the twin-screw extruder via the feed hopper. Alternatively, one or more components may be mixed into the composition by feeding directly into the extruder at the inlet and/or downstream via sidestuffers. Such additives can also be mixed with the desired polymeric resin into a masterbatch and fed to the extruder. The extruder is generally operated at a temperature higher than that required to flow the composition. The extrudate was immediately quenched in a water bath and pelleted. When the extrudate is cut, the pellets so prepared can be a quarter inch long or smaller as desired. Such shot can be used for subsequent molding, molding or forming.

The amount of phosphonium sulfonate salt added to the thermoplastic resin is an amount effective to reduce or eliminate static charge and can vary within certain limits. It has been found that if too little of the antistatic substituted phosphonium sulfonate salt is added to the resin, there may also be a tendency for static charges to build up on articles made of the resin. If the amount of antistatic additive added is too high, it is not economical to add these amounts, and at a certain level it starts to adversely affect other properties of the resin. Relative to the total weight of antistatic agent and polymer, adopt about 0.01 to about 10% by weight, especially about 0.2 to about 2.0% by weight, more especially about 0.5 to about 1.5% by weight of antistatic agent and about 90 to about 99.99% by weight % by weight, especially from about 99 to about 99.8% by weight, more specifically from about 98.5 to about 99.5% by weight of polymer, results in a thermoplastic composition with enhanced antistatic properties. In one embodiment, to obtain good results with transparent polycarbonate grades via such internal application methods, the amount of antistatic agent used is generally from about 0.01 to about 3.0% by weight of the molding composition, especially about 0.1 to about 1.5% by weight, or especially about 0.4 to about 0.8% by weight. The antistatic agent provided herein has stronger heat resistance, and its addition amount is less than traditional ionic surfactants such as alkyl phosphonium sulfonate, and the resin composition has good transparency and mechanical properties.

The phosphonium salts described above are also useful in preparing thermoplastic polymer compositions with improved thermal stability. In one embodiment, after aging for 936 hours at 130° C., the polycarbonate composition containing the antistatic agent prepared by one of the above methods has a yellowness index of less than about 15, especially less than about 10, more particularly is lower than about 8, and even more particularly lower than about 6.

For example, thermoplastic compositions containing the antistatic agent can be used to form articles such as computer and business machine housings such as monitor housings, hand-held electronic device housings such as cell phones, junction boxes and lighting fixture parts housings, decorative objects, household appliances, Roofs, greenhouses, solariums, swimming pool fences, carrier tapes for semiconductor packaging materials, automotive parts, etc.

The thermoplastic composition can be converted into articles using processes such as film and sheet extrusion, injection molding, gas-assisted injection molding, extrusion molding, compression molding, and blow molding. Film and sheet extrusion processes may include, but are not limited to, melt casting, blown film extrusion, and calendering. Coextrusion and lamination processes can be used to form composite multilayer films or sheets. A further layer or layers of coatings may also be applied to the one or more layers of the substrate to impart additional properties such as scratch resistance, UV resistance, aesthetic appeal, and the like. Coatings can be applied via coating techniques such as rolling, spraying, dipping, brushing or flow coating. Alternatively, films or sheets may be prepared by casting a suspension of the thermoplastic composition in a suitable solvent onto a substrate, conveyor belt or roll, followed by removal of the solvent.

Oriented films can be produced by blown film extrusion or by stretching cast or calendered films using conventional stretching techniques near the heat distortion temperature. For example, a radial stretching pantograph can be applied for multi-axial simultaneous stretching; an x-y stretching pantograph can be used for simultaneous or sequential stretching in the planar x-y direction. Units with uniaxial stretching components can also be used, such as machines equipped with differential roll components for machine direction stretching and tenter frame components for transverse stretching, to achieve uniaxial and biaxial stretching stretch.

The thermoplastic composition of the present invention may also be converted into a multilayer sheet comprising a first sheet and a second sheet, the first sheet having a first face and a second face, the first sheet comprising a thermoplastic polymer, and Wherein the first face of the first sheet is placed on the first face of a plurality of ribs (rib); the second sheet has a first face and a second face, wherein the second sheet contains a thermoplastic polymer, wherein the first face of the second sheet One side rests on the second face of the plurality of ribs, and wherein the first face of the plurality of ribs is opposite the second face of the plurality of ribs.

The films and sheets described above can be further thermoplastically processed into shaped articles via forming and molding processes including, for example, thermoforming, vacuum forming and pressure forming, injection molding and compression molding. It is also possible to inject a thermoplastic resin onto a single or multilayer film or sheet substrate, for example by providing a single or multilayer thermoplastic substrate optionally with one or more colors on the surface (e.g. by screen printing or transfer dyeing). ;Conforming the substrate to the shape of the mold, such as molding and forming the substrate into a three-dimensional shape, loading the substrate into a mold whose surface conforms to the three-dimensional shape of the substrate; injecting thermoplastic resin into the mold cavity after the substrate , to make multi-layer shaped articles to (i) form a permanently bonded three-dimensional article, or (ii) transfer a pattern or aesthetic effect from a printed substrate to spraying the resin and removing the printed substrate to give the molded Resin aesthetic effect.

Those skilled in the art will also appreciate that known curing and surface modification processes including, but not limited to, heat setting, texturing, embossing, corona treatment, flame treatment, plasma treatment and/or vacuum deposition will further Applied to the above items to change the surface appearance and give the item additional functionality.

Accordingly, another embodiment of the present invention relates to articles, sheets and films prepared from the thermoplastic compositions described above.

The phosphonium salt (1) can be produced rapidly and with high purity by the method described above. In one embodiment, the total amount of ionic impurities is less than about 650 parts per million (ppm), more specifically less than about 500 ppm, even more specifically less than about 100 ppm, more specifically less than about 50 ppm, most specifically less than about 10 ppm . In yet another embodiment, the product contains less than about 5 ppm alkali metal, preferably less than about 4 ppm alkali metal. In yet another embodiment, the product contains less than about 500 ppm, preferably less than about 100 ppm, more preferably less than about 50 ppm, most preferably less than about 10 ppm halide. Other ionic impurities, such as phosphate or sulfate, are individually present in amounts less than about 100 ppm, preferably less than about 50 ppm, most preferably less than about 10 ppm.

This method is further illustrated by the following non-limiting examples.

Example

The sample was scanned from 50°C to 100°C at a scanning speed of 10°C/min for differential scanning calorimetry (DSC) measurement. The samples were scanned from 50°C to 600°C at a scanning speed of 10°C/min for thermogravimetric analysis (TGA). The ion content of the salts was determined by ion chromatography. Yellowness Index (YI) was determined via a Gretag McBeth Color-Eye 7000A using Propalette software.

系统处理的水(MilliQ

是Millipore公司的商标)。“TBPBr”指溴化四丁基鏻。In the following examples, "MQ water" refers to deionized and MilliQ

System treated water (MilliQ

is a trademark of Millipore Corporation). "TBPBr" refers to tetrabutylphosphonium bromide.

Example 1

First, 5.00 g (MW 302, 16.55 mmol) of perfluorobutanesulfonyl fluoride ("A") was weighed into a 100-mL 2-neck round bottom beaker, stirred with a magnetic stirrer and refluxed in an 85 °C oil bath.

Next, 0.95 g of lithium hydroxide (LiOH) (24.83 mmol) was added to 25 mL of MQ water and dissolved, then slowly added to A. The mixture was then refluxed for about one hour, and another 25 mL of MQ water was added and stirred. The undissolved residue was filtered off, collected in another 100-mL 2-neck round bottom beaker, and heated again in an oil bath at 85°C. 8.43 grams of TBPBr (24.83 mmol) were then dissolved in 25 mL of MQ water and slowly added to the filtrate to generate the antistatic agent product. After all the dissolved TBPBr was added, the mixture was stirred for an additional 15 minutes. The mixture is then cooled, preferably in an ice/water bath, and the water is decanted. Next, 100 mL of MQ water was added, and stirred for 15 minutes while heating in an 85° C. oil bath. The mixture was then cooled to room temperature and the product was isolated by filtration and rinsed with 25 mL of MQ water. The product was dried in a vacuum oven at 50°C. Theoretical yield is 9.24 g of antistatic agent; 3.8 g are obtained.

Example 2

First, 54.8 grams (180.837 mmol) of lithium perfluorobutanesulfonate ("Li Rimar") was added and dissolved in 300 mL of MQ water at room temperature, and 60.8 grams (179.062 mmol) of TBPBr was added and dissolved in 200 mL of MQ water at room temperature . Filter the TBPBr solution, then stir it with a spiral stirrer, and gradually pour it into the Li Rimar salt solution to generate an antistatic agent product. After all of the TBPBr had been added, the reaction mixture was stirred for an additional 15 minutes. At the end of the reaction, the antistatic agent product was separated by filtration, and washed with 50mL of MQ water to remove most of the impurities. Further purification was accomplished by suspending the antistatic product in MQ water and heating to 80°C, stirring for a few minutes, and cooling the mixture to recrystallize the antistatic product. The antistatic agent product can then be isolated by filtration and dried in a vacuum drying oven at 50°C. Theoretical yield is 100.0 g of antistatic agent; 87.1 g are obtained.

Example 3

First, 5.00 g (MW 302, 16.55 mmol) of perfluorobutanesulfonyl fluoride ("A") was weighed into a 100-mL 2-neck round bottom beaker, stirred with a magnetic stirrer, and refluxed in an 85 °C oil bath.

Then slowly add 32% by weight NaOH solution, which is 2.4 times the amount of A. That is, 39.72 mmol corresponds to 1.58 grams of NaOH (4.94 grams of a 32% by weight solution). Then the mixture was refluxed for 1 hour, and then 50 mL of MQ water was added and stirred until all dissolved. Next, 5.62 grams of TBPBr (16.55 mmol) was dissolved in 25 mL of MQ water and slowly added to the solution to generate the antistatic agent product. After addition of all dissolved TBPBr, the mixture was stirred for an additional 15 minutes. Next, the mixture is cooled, preferably in an ice/water bath, and the water is decanted. Then add 100mL of MQ water, and stir for 15 minutes while heating in an oil bath at 85°C. Cool the mixture to room temperature, isolate the antistatic agent product by filtration, and rinse with 25 mL of MQ water. The antistatic agent product was then dried in a vacuum drying oven at 50°C. Theoretical yield is 9.24 g of antistatic agent; 5.8 g are obtained.

Example 4

First, 5.77 grams (18.083 mmol) of sodium perfluorobutanesulfonate ("Na Rimar") was added and dissolved in 50 mL of MQ water at room temperature, and 6.08 grams (17.906 mmol) of TBPBr was added and dissolved in 20 mL of MQ water. Filter the TBPBr solution, then stir it with a strong magnetic stirrer, and gradually pour it into the Na Rimar salt solution to generate an antistatic agent product. After all of the TBPBr had been added, the reaction mixture was stirred for an additional 15 minutes. When the reaction ended, the antistatic agent product was separated by filtration, and washed with 50mL of MQ water to remove most of the impurities. Further purification can be achieved by stirring the antistatic product in MQ water, heating to 80°C, stirring for a few minutes, and cooling the mixture to recrystallize the antistatic product. Then the antistatic agent product was separated by filtration, and dried in a vacuum drying oven at 50°C. Theoretical yield is 10.0 g of antistatic agent; 8.10 g are obtained.

Example 5

First, weigh 5.00 g (MW 302, 16.55 mmol) of perfluorobutanesulfonyl fluoride ("A") into a 100-mL 2-neck round bottom beaker, stir with a magnetic stirrer, and reflux in an oil bath at 85 °C . Next, 4.46 g of a 50 wt% KOH solution were slowly added to yield 2.4 equivalents of KOH (2.23 g, 39.72 mmol) (4.46 g of a 50 wt% solution). The mixture was refluxed for 1 hour, and then 75 mL of ethanol/MQ (volume ratio 3/4) was added and stirred until completely dissolved. Next, 5.56 grams of TBPBr (16.38 mmol) was dissolved in 25 mL of MQ water and slowly added to the solution to generate the antistatic agent product. After addition of all dissolved TBPBr, the mixture was stirred for an additional 15 minutes before being allowed to cool to room temperature. Use 75mL of dichloromethane to extract the antistatic agent product through a separatory funnel, and wash with 50mL of MQ water for 3 times. The organic layer was removed in vacuo (50 °C, _pstart = 475 mbar and _pend = 125 mbar). Further purification can be achieved by stirring the antistatic product in MQ water, heating to 80°C, stirring for a few minutes, and cooling the mixture to recrystallize the antistatic product. Then, the antistatic agent product was separated by filtration, and dried in a vacuum oven at 50°C. Theoretical yield is 9.24 g of antistatic agent; 6.04 g are obtained.

Comparative Example 6

First, at room temperature, 6.06 g (17.9 mrnol) of potassium perfluorobutanesulfonate ("K Rimar") was added and dissolved in 75 mL of an aqueous solution with a volume ratio of ethanol/MQ of 3/4, and 6.01 g (17.7 mmol) TBPBr was added and dissolved in 25 mL of MQ water. While stirring, the TBPBr solution was gradually poured into the KRimar salt solution to generate an antistatic agent product. After all of the TBPBr had been added, the reaction mixture was stirred for an additional 15 minutes. Then use 75mL of dichloromethane to extract the antistatic agent product through a separatory funnel, and wash with 50mL of MQ water for 3 times. The organic layer was removed in vacuo (50 °C, _pstart = 475 mbar and _pend = 125 mbar). Further purification can be achieved by stirring the antistatic product in MQ water, heating to 80°C, stirring for a few minutes, and cooling the mixture to recrystallize the antistatic product. Then, the antistatic agent product was separated by filtration, and dried in a vacuum oven at 50°C. Theoretical yield is 10.0 g of antistatic agent; 8.91 g are obtained.

Example 7

First, weigh 5.00 g (MW 302, 16.55 mmol) of A into a 100-mL 2-neck round bottom beaker, stir with a magnetic stirrer, and reflux in an 85 °C oil bath. Next, 10.98 g (39.72 mmol) of 40% by weight tetrabutylphosphonium hydroxide were added. The mixture was refluxed for another 1 hour. Then 50 mL of MQ water was added and stirred for an additional 15 minutes. The mixture is then cooled, preferably in an ice/water bath, and the water is decanted. Then add 100mL of MQ water, and stir for 15 minutes while heating in an oil bath at 85°C. Then the mixture was cooled to room temperature, and the antistatic agent product was separated by filtration, washed with 25 mL of MQ water. Next, the antistatic agent product was dried in a vacuum drying oven at 50°C. The theoretical yield was 9.24 g of antistatic agent; 7.4 g was obtained.

 FASP-I的全氟化丁磺酸盐抗静电剂。经差示扫描量热法(DSC)确定熔点。经热重分析(TGA)确定抗静电剂的热降解，在该温度下进行测量，其中先测定降解。Table 1 provides the properties of the antistatic agents prepared through the various synthetic routes detailed in Examples 1-7 above. The reference sample was obtained from Dupont under the trade name Zonyl

FASP-I perfluorobutanesulfonate antistatic agent. Melting points were determined by differential scanning calorimetry (DSC). The thermal degradation of the antistatic agent was determined by thermogravimetric analysis (TGA), the temperature at which the measurement was performed, wherein the degradation was determined first.

Table 1.

As can be seen from the above table 1, the method of embodiment 3 is particularly advantageous because of the high yield. In addition, the synthetic steps are simple.

Table 2 shows that the antistatic agents prepared through different synthetic routes detailed in Examples 1-2 contain less ionic impurities after washing with water at 80°C.

Table 2

Certain by-products commonly found in antistatic agents are known to be detrimental to the properties of hybrid thermoplastic polymers such as polycarbonate. For example, as shown in Figure 1, the presence of increasing amounts of bromine resulted in increased yellowing of polycarbonate after heat aging at 130°C for 936 hours. Table 3 further shows the change in YI (ΔYI) of polycarbonates containing specified amounts of ionic impurities after heat aging. Spotting was observed in heat aged polycarbonate, which may be caused by potassium and sodium impurities.

table 3.

In order to determine the effect of washing the antistatic agent of the above-mentioned embodiment, take by weighing 10.02 grams of the unwashed antistatic agent prepared in the above-mentioned embodiment 2 in a 150mL beaker, add 100mL MQ water. Stir it so that the antistatic agent is evenly dispersed in the water, and continue stirring for 15 minutes at room temperature. The antistatic agent was then filtered, dried and tested for ionic impurities.

In the second test, 10.06 grams of the unwashed antistatic agent prepared in Example 2 above was weighed into a 150 mL beaker, and 100 mL of MQ water was added thereto. Stir well to disperse the antistatic agent evenly in the water, and continue stirring at 80°C for 15 minutes. The antistatic agent of Example 2 melts at this temperature and forms an emulsion while stirring. The mixture was cooled and the solid was filtered off, dried and tested for ionic purity. Table 4 shows the yield after washing, and Table 5 shows the ion chromatography results.

Table 4

table 5

Antistatic agents can be synthesized according to all the examples above. Washing the antistatic agent with water at room temperature or 80°C washes away any ionic impurities.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. The terms "first", "second", etc. herein do not denote any order, quantity or importance, but are used to distinguish one element from another. Endpoints of entire ranges listing the same property may combine and encompass the listed endpoints. The modifier "about" applied to a quantity is inclusive of the stated value and has the meaning dictated by the context (eg, includes the degree of error associated with measurement of the particular quantity). All references are incorporated herein by reference.

While typical embodiments have been set forth for purposes of illustration, the foregoing description should not be considered as limiting the scope herein. Accordingly, various modifications, modifications, and substitutions are possible to those skilled in the art without departing from the spirit and scope herein.

Claims (21)

1. a method for preparing the phosphonium sulfonate salt of general formula (1):

wherein each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than 0.90; p is 0 or 1, and q and r are integers from 0 to 7, provided that q+r is less than 8, and if p is not 0 , then r is greater than 0; each R is the same or different hydrocarbon groups containing 1-18 carbon atoms, and the method includes: In an aqueous medium, a compound of general formula (4) is mixed with a compound of general formula (5): Wherein the meanings of X, p, q and r are the same as those in formula (1), (R) ₄ P-OH (5) wherein R has the same meaning as in formula (1); and, Isolate the phosphonium sulfonate product of formula (1). 2. The method of claim 1, wherein X is fluorine; Z bromine or chlorine; Three R groups are identical aliphatic hydrocarbon groups containing 1-8 carbon atoms or aromatic hydrocarbon groups containing 6-12 carbon atoms, the fourth Each R group is a hydrocarbyl group containing 1-18 carbon atoms. 3. The method of claim 2, wherein p is zero. 4. The method of claim 1, wherein the sulfonate is perfluoromethanesulfonate, perfluoroethanesulfonate, perfluoropropanesulfonate, perfluorobutanesulfonate, perfluoropentanesulfonate, perfluorohexylsulfonate, perfluorohexanesulfonate, Fluoroheptyl sulfonate, perfluorooctyl sulfonate, or a combination containing at least one of the foregoing sulfonates; wherein the phosphonium is tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, triethylphosphonium Butylmethylphosphonium, tributylethylphosphonium, trioctylmethylphosphonium, trimethylbutylphosphonium, trimethyloctylphosphonium, trimethyldodecylphosphonium, trimethylstearylphosphonium, three Ethyloctylphosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, and tributylbenzylphosphonium, or a combination comprising at least one of the foregoing phosphoniums. 5. The method of claim 4, wherein the sulfonate is perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexylsulfonate, perfluoroheptanesulfonate, perfluorooctylsulfonate or comprises at least one of the aforementioned organic sulfonates A combination of acid anions, the phosphonium being tetrabutylphosphonium. 6. The method of claim 5, wherein the molar ratio of the compound of formula (4) to the compound of formula (3) is 1:2.01-1:3. 7. The method of claim 1, wherein the aqueous medium comprises less than 1 volume percent of the non-aqueous medium. 8. The method of claim 1, wherein the phosphonium sulfonate product is precipitated from the aqueous medium. 9. The method of claim 4, wherein the phosphonium is selected from the group consisting of tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, and tributylbenzylphosphonium. 10. A method for preparing a phosphonium sulfonate salt of general formula (1):

wherein each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than 0.90; p is 0 or 1, and q and r are integers from 0 to 7, provided that q+r is less than 8, and if p is not 0 , then r is greater than 0; each R is the same or different hydrocarbon groups containing 1-18 carbon atoms, and the method includes: In an aqueous medium, sodium hydroxide and/or lithium hydroxide; The compound of general formula (4) is mixed with the compound of general formula (3): Wherein X, p, q and r have the same meaning as in formula (1); (R) ₄ PZ (3) wherein Z is halogen and R is as defined above; and The phosphonium sulfonate of formula (1) is isolated. 11. The method of claim 10, wherein the molar ratio of the compound of formula (4) to the compound of formula (3) is 1:2.01-1:3. 12. The method of claim 10, wherein X is fluorine; Z is bromine or chlorine; three R groups are identical aliphatic hydrocarbon groups containing 1-8 carbon atoms or aromatic hydrocarbon groups containing 6-12 carbon atoms, the first The four R groups are hydrocarbyl groups containing 1-18 carbon atoms. 13. The method of claim 10, wherein p is zero. 14. The method of claim 10, wherein the sulfonate is perfluoromethanesulfonate, perfluoroethanesulfonate, perfluoropropanesulfonate, perfluorobutanesulfonate, perfluoropentanesulfonate, perfluorohexylsulfonate, perfluoro Heptylsulfonate, perfluorooctylsulfonate, or a combination containing at least one of the foregoing sulfonates; wherein the phosphonium is tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium Phosphonium, Tributylethylphosphonium, Trioctylmethylphosphonium, Trimethylbutylphosphonium, Trimethyloctylphosphonium, Trimethyldodecylphosphonium, Trimethylstearylphosphonium, Triethylphosphonium octylphosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, and tributylbenzylphosphonium, or a combination comprising at least one of the foregoing phosphoniums. 15. The method of claim 14, wherein the sulfonate is perfluoromethanesulfonate, perfluorobutanesulfonate, perfluorohexylsulfonate, perfluoroheptanesulfonate, perfluorooctylsulfonate or comprises at least one of the foregoing organic sulfonate A combination of anions, the phosphonium being tetrabutylphosphonium. 16. The method of claim 10, wherein the aqueous medium comprises less than 1 volume percent of the non-aqueous medium. 17. The method of claim 10, wherein the phosphonium sulfonate product is precipitated from said aqueous medium. 18. The method of claim 10, wherein lithium hydroxide and/or sodium hydroxide is added to the compound of formula (4) prior to the compound of formula (3). 19. The method of claim 18, wherein the product after adding lithium hydroxide and/or sodium hydroxide is the corresponding basic sulfonate (2)

Wherein M is Li or Na, and each X is independently halogen or hydrogen, provided that the molar ratio of halogen to hydrogen is greater than 0.90; p is 0 or 1, q and r are integers from 0 to 7, provided that q+r is less than 8, And if p is not 0, then r is greater than 0. 20. The method of claim 19, further comprising isolating salt (2) prior to adding the compound of formula (3). 21. The method of claim 14, wherein the phosphonium is selected from the group consisting of tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, and tributylbenzylphosphonium.

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