JP2003277347A - Perfluoroalkylnaphthalenesulfonic acid salt, method for producing the same, dispersant and antistatic agent for synthetic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new perfluoroalkylnaphthalenesulfonic acid salt useful as a dispersant for pigment, an antistatic agent for a synthetic polymer, etc., and to provide a method for producing the same. <P>SOLUTION: The perfluoroalkylnaphthalenesulfonic acid salt is represented by general formula I (n is an integer of 1-7; M is a lithium atom, a sodium atom or a potassium atom). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel perfluoroalkylnaphthalene sulfonate, a method for producing the same, a dispersant comprising the perfluoroalkylnaphthalene sulfonate, and an antistatic agent for synthetic polymers.

[0002]

2. Description of the Related Art Conventionally, various anionic surfactants have been used as pigments, dyes, agricultural chemicals, and dispersants for emulsion polymerization. As such an anionic surfactant,
Substituted aromatic sulfonates such as alkyl naphthalene sulfonate and dialkyl naphthalene sulfonate are also known (JP-A-13-151604, JP-A-12-313).
824, JP-A-5-15762). However, in these conventional substituted aromatic sulfonates, since the substituents of all of them are hydrocarbon groups and are lipophilic, coating compositions, agrochemical compositions, and When the emulsion polymer is required to have dispersibility as well as oleophobicity such as oil repellency, antifouling property and solvent durability, there is a problem that such requirements cannot be met. A substituted aromatic sulfonate having a hydrocarbon group as a substituent is also known as an antistatic agent for synthetic polymers (Japanese Patent Laid-Open No. 11-35777,
JP-A-10-81830), a synthetic polymer material using these as an antistatic agent, an antistatic property and an oil repellency,
When the oleophobic property such as antifouling property and non-adhesion preventing property is required, there is a problem that the request cannot be met as in the case described above.

[0003]

The problem to be solved by the present invention is to provide a novel perfluoroalkylnaphthalene sulfonic acid which can be used as a dispersant or an antistatic agent which meets such requirements even when oleophobicity is required. A salt and a method for producing the salt are provided.

[0004]

The present invention for solving the above problems relates to a perfluoroalkylnaphthalene sulfonate represented by the following formula (1).

[0005]

[Formula 1]

In equation 1, n: integer from 1 to 7 M: lithium atom, sodium atom or potassium atom

The present invention also relates to a method for producing the above-mentioned perfluoroalkylnaphthalenesulfonate, a dispersant comprising the perfluoroalkylnaphthalenesulfonate, and an antistatic agent for synthetic polymers.

In the perfluoroalkylnaphthalene sulfonate represented by the formula 1, 1) lithium = 5- (2,2,3,3-tetrafluoropropyl) -2 when M in the formula 1 is lithium. -Naphthalene sulfonate, lithium = 5- (2,2,3,3,4,4-hexafluorobutyl) -2-naphthalene sulfonate, lithium =
5- (2,2,3,3,4,4,5,5-octafluoropentyl) -2-naphthalene sulfonate, lithium = 5- (2,2,3,3,4,4,5,5 , 6,6-decafluorohexyl) -2-naphthalene sulfonate,
Lithium = 5- (2,2,3,3,4,4,5,5,5
6,6,7,7-dodecafluoroheptyl) -2-naphthalene sulfonate, lithium = 5- (2,2,3,3
3,4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyl) -2-naphthalene sulfonate, lithium = 5- (2,2,3,3,4,4) , 5,
5,6,6,7,7,8,8,9,9-hexadecafluorononyl) -2-naphthalene sulfonate, 2) Formula 1
When M is sodium, sodium = 5-
(2,2,3,3-tetrafluoropropyl) -2-naphthalene sulfonate, sodium = 5- (2,2,
3,3,4,4-hexafluorobutyl) -2-naphthalene sulfonate, sodium = 5- (2,2,3,
3,4,4,5,5-octafluoropentyl) -2-
Naphthalene sulfonate, sodium = 5- (2,2,
3,3,4,4,5,5,6,6-decafluorohexyl) -2-naphthalene sulfonate, sodium = 5-
(2,2,3,3,4,4,5,5,6,6,7,7-
Dodecafluoroheptyl) -2-naphthalene sulfonate, sodium = 5- (2,2,3,3,4,4,5,5
5,6,6,7,7,8,8-tetradecafluorooctyl) -2-naphthalene sulfonate, sodium = 5
-(2,2,3,3,4,4,5,5,6,6,7,
7,8,8,9,9-hexadecafluorononyl) -2
-Naphthalene sulfonate, 3) potassium = 5- (2,2,3,3-tetrafluoropropyl) -2-naphthalene sulfonate when M in formula 1 is potassium,
Potassium = 5- (2,2,3,3,4,4-hexafluorobutyl) -2-naphthalene sulfonate, potassium = 5- (2,2,3,3,4,4,5,5-octa Fluoropentyl) -2-naphthalene sulfonate, potassium = 5- (2,2,3,3,4,4,5,5,6,6-
Decafluorohexyl) -2-naphthalene sulfonate, potassium = 5- (2,2,3,3,4,4,5)
5,6,6,7,7-dodecafluoroheptyl) -2-
Naphthalene sulfonate, potassium = 5- (2,2,
3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyl) -2-naphthalene sulfonate, potassium = 5- (2,2,3,3,4 , 4, 5,
5,6,6,7,7,8,8,9,9-hexadecafluorononyl) -2-naphthalene sulfonate.

The perfluoroalkylnaphthalene sulfonate represented by the formula 1 can be produced by various methods, but preferable production methods include the following first step, second step and third step. . First step: a step in which naphthalene and sulfuric acid having a concentration of 90 to 100% are subjected to a sulfonation reaction at a reaction temperature of 140 to 170 ° C. to produce naphthalenesulfonic acid. Second step: The naphthalene sulfonic acid produced in the first step and a perfluoroalkyl alcohol represented by the following formula 2 are subjected to a perfluoroalkylation reaction at a temperature of 0 to 150 ° C. using an acid catalyst to give the following: A step of producing a perfluoroalkylnaphthalenesulfonic acid represented by Formula 3. Third step: a step of neutralizing the perfluoroalkylnaphthalenesulfonic acid produced in the second step and the alkali in an aqueous alcohol solution to produce a perfluoroalkylnaphthalenesulfonate.

[0010]

[Formula 2]

[Formula 3]

In equation 3, n: integer from 1 to 7

In the first step, naphthalene and sulfuric acid are subjected to a sulfonation reaction to produce naphthalenesulfonic acid.
Here, sulfuric acid having a concentration of 90 to 100% is used. The charging ratio of naphthalene and sulfuric acid is usually naphthalene / sulfuric acid = 25/75 to 60/40 (molar ratio), but it is preferably 30/70 to 50/50 (molar ratio). The sulfonation reaction is carried out at a temperature of 140 to 170 ° C, preferably 150 to 160 ° C. The production of naphthalenesulfonic acid can be confirmed by analysis by high performance liquid chromatography. Such first
In the step, a reaction solution containing the produced naphthalenesulfonic acid is obtained, which can be directly used in the second step.

In the second step, the naphthalenesulfonic acid produced in the first step and the perfluoroalkyl alcohol represented by the formula 2 are perfluoroalkylated to produce the perfluoroalkylnaphthalenesulfonic acid represented by the formula 3. The charging ratio of naphthalene sulfonic acid and perfluoroalkyl alcohol is usually naphthalene sulfonic acid / perfluoroalkyl alcohol = 25.
/ 75 to 60/40 (molar ratio), but 30/70 to
It is preferably 50/50 (molar ratio). In the second step, an acid catalyst is used in the perfluoroalkylation reaction. Examples of such an acid catalyst include anhydrous aluminum chloride, anhydrous zinc chloride, boron trifluoride, hydrofluoric acid, sulfuric acid, etc. Among them, anhydrous aluminum chloride is preferable.
The amount of the acid catalyst used is usually 0.0001 to 2 mol per mol of the perfluoroalkyl alcohol.
Further, the perfluoroalkylation reaction is carried out at a temperature of 0 to 150 ° C, preferably 25 to 80 ° C. The production of perfluoroalkylnaphthalenesulfonic acid can be confirmed by analysis by high performance liquid chromatography. In the second step, a reaction liquid containing the produced perfluoroalkylnaphthalenesulfonic acid is obtained, which can be directly used in the third step.

In the third step, the perfluoroalkylnaphthalenesulfonic acid produced in the second step and the alkali are neutralized in an aqueous alcohol solution to produce a perfluoroalkylnaphthalenesulfonate. The amount of alkali used in the neutralization reaction is usually an amount corresponding to 1 to 1.1 equivalents of the acid value of the reaction solution containing the perfluoroalkylnaphthalenesulfonic acid produced in the second step.
Examples of the alkali include hydroxides, carbonates, alcoholates and the like of the atom represented by M in Formula 1. Examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium ethylate, sodium ethylate, potassium ethylate and the like. The neutralization reaction is usually performed at a temperature of 0 to 90 ° C. by adding the reaction solution containing the perfluoroalkylnaphthalenesulfonic acid generated in the second step to an alcohol aqueous solution in which an alkali is dissolved with stirring. Thus, the perfluoroalkylnaphthalene sulfonate represented by the formula 1 is produced. The pure perfluoroalkylnaphthalene sulfonate represented by Formula 1 is obtained by separating and purifying from the reaction solution obtained in the third step described above. For example, first, sodium sulfate produced as a by-product is filtered off from the reaction solution to obtain a filtrate containing a perfluoroalkylnaphthalene sulfonate. Next, the solvent is distilled off from this filtrate under reduced pressure to obtain a solid content. Finally, the solid content is purified by recrystallization or column chromatography to obtain a pure perfluoroalkylnaphthalenesulfonate.

Another preferred method for producing the perfluoroalkylnaphthalene sulfonate represented by formula 1 is as follows:
A manufacturing method including the following Step A, Step B and Step C may be mentioned. Step A: Step of producing naphthalene and perfluoroalkyl alcohol represented by Formula 2 by perfluoroalkylation reaction using an acid catalyst at a temperature of 0 to 150 ° C. to produce perfluoroalkylnaphthalene Step B: produced in step A The perfluoroalkylnaphthalene thus produced and fuming sulfuric acid are subjected to a sulfonation reaction at a temperature of 140 to 170 ° C. to produce a perfluoroalkylnaphthalenesulfonic acid represented by the formula 3. Step C step: perfluoroalkyl produced in step B Step of neutralizing naphthalene sulfonic acid and alkali in an aqueous alcohol solution to produce perfluoroalkylnaphthalene sulfonate

In step A, naphthalene and the perfluoroalkyl alcohol represented by the formula 2 are perfluoroalkylated to produce perfluoroalkylnaphthalene. The charging ratio of naphthalene and perfluoroalkyl alcohol is usually naphthalene / perfluoroalkyl alcohol = 25/75 to 70/30 (molar ratio), but 30/70 to 50/50 (molar ratio) is preferable. . In step A, an acid catalyst is used in the perfluoroalkylation reaction. As such an acid catalyst,
Anhydrous aluminum chloride, anhydrous zinc chloride, boron trifluoride,
Examples thereof include hydrofluoric acid and sulfuric acid, with anhydrous aluminum chloride being preferred. The amount of the acid catalyst used is usually 0.000 per mol of the perfluoroalkyl alcohol.
The ratio is 1 to 2 mol. The perfluoroalkylation reaction is carried out at a temperature of 0 to 150 ° C.
It is preferably carried out at a temperature of ° C. The production of perfluoroalkylnaphthalene can be confirmed by analysis by high performance liquid chromatography. In the step A, a reaction liquid containing the produced perfluoroalkylnaphthalene is obtained, so that the perfluoroalkylnaphthalene as a product is separated from the reaction liquid, and this is supplied to the step B. For example, water is added to the reaction solution while cooling it to 10 ° C. or lower to deactivate the acid catalyst and to separate the water layer and the oil layer, and then the water layer is removed and the oil layer is washed with water, and then the oil layer is removed. Is subjected to dehydration treatment and subjected to step B.

In step B, the perfluoroalkylnaphthalene produced in step A is subjected to a sulfonation reaction with fuming sulfuric acid to produce perfluoroalkylnaphthalenesulfonic acid. The charging ratio of perfluoroalkylnaphthalene and fuming sulfuric acid is usually perfluoroalkylnaphthalene / fuming sulfuric acid = 25/75 to 60/40 (molar ratio), but 30/70 to 50/50 (molar ratio). Is preferred. The sulfonation reaction is carried out at a temperature of 140 to 170 ° C, preferably 150 to 160 ° C. The production of perfluoroalkylnaphthalenesulfonic acid can be confirmed by analysis by high performance liquid chromatography. In step B, a reaction liquid containing the produced perfluoroalkylnaphthalenesulfonic acid is obtained, which can be directly used in step C.

In step C, the perfluoroalkylnaphthalene sulfonic acid produced in step B is neutralized with an alkali in an aqueous alcohol solution to produce a perfluoroalkylnaphthalene sulfonate. The amount of the alkali used in the neutralization reaction is usually an amount corresponding to 1 to 1.1 equivalents of the acid value of the reaction solution containing the perfluoroalkylnaphthalenesulfonic acid produced in the step B. The kind of the alkali and the operation of the neutralization reaction are the same as those described above for the third step. Thus, the perfluoroalkylnaphthalene sulfonate represented by the formula 1 is produced. The pure perfluoroalkylnaphthalene sulfonate represented by the formula 1 is obtained by separating and purifying from the reaction solution obtained in the step C described above. The separation and purification operations are the same as described above.

The perfluoroalkylnaphthalene sulfonate represented by the formula 1 is used as a dispersant for pigments, dyes, agricultural chemicals, emulsion polymerization, and an antistatic agent for synthetic polymers such as thermoplastic resins and thermosetting resins. Widely available as
It is particularly useful as a dispersant for pigments and an antistatic agent for synthetic polymers.

The pigment dispersant of the present invention comprising the perfluoroalkylnaphthalene sulfonate represented by formula 1 is
It imparts excellent dispersibility to a coating composition using the same, and at the same time imparts excellent oleophobicity such as oil repellency, antifouling property and solvent durability to the coated surface. Pigments to which the pigment dispersant is applied include titanium dioxide, iron oxide, zinc oxide,
Inorganic pigments such as lead chromate and carbon black, dye-based pigments such as azo, thioindigo and anthraquinone, copper phthalocyanine, nuclear halogenated derivatives thereof, phthalocyanine pigments such as copper tetraphenylphthalocyanine and octaphenylphthalocyanine, dianthraquinonyl red, indane Threnic pigments such as tron blue, indigo pigments such as thioindigocobalt, perinone pigments such as perinone orange, perylene maroon, perylene red, perylene pigments such as perylene violet, phthalone pigments such as quinophthalo yellow, carbazole. Dioxazine-based pigments such as violet, quinacridone-based pigments such as unsubstituted quinacridone, quinacridone magenta, dichloroquinacridone and quinacridone scarlet, and isoindoline yellow R Dorinon pigments, metal complex pigments such as copper azomethine yellow, diketopyrrolopyrrole pigments such as DPP Red, and organic pigments such as methine-azomethine pigments.

As a method for applying the pigment dispersant of the present invention to a pigment, a known method can be applied. For example, in the case of producing a coating composition using a granular solid of a pigment, 1) the pigment dispersant of the present invention is added to the pigment and dispersed by a disperser such as a paint conditioner or a ball mill, and then a resin is further added. And 2) a method of dispersing the mixture of the pigment dispersant of the present invention and a pigment and a resin at once with a disperser such as a paint conditioner or a ball mill. The use amount of the pigment dispersant of the present invention is usually 0.1 to 5 parts by weight with respect to 100 parts by weight of the pigment.

The pigment dispersant of the present invention can be used alone or in combination with a known pigment dispersant. The pigment dispersant of the present invention can also be used together with additives such as a wetting agent, a leveling agent, a rheology control agent and a silane coupling agent.

The antistatic agent for synthetic polymers of the present invention comprising the perfluoroalkylnaphthalene sulfonate represented by the formula 1 imparts excellent antistatic property to the synthetic polymer material using the same, and at the same time, has oil repellency, Provides excellent oleophobicity such as antifouling property and non-adhesiveness. Examples of synthetic polymer materials to which such an antistatic agent for synthetic polymers is applied include polyester, nylon, polypropylene, polycaprolactone,
Examples thereof include synthetic polymer films and sheets formed from synthetic polymers such as acrylic resin, and synthetic fibers such as filament yarns and staple fibers.

The method for applying the antistatic agent for synthetic polymer of the present invention to a synthetic polymer film or sheet is as follows: 1) after adding the antistatic agent for synthetic polymer of the present invention to a synthetic polymer, And 2) a method of applying the antistatic agent for synthetic polymer of the present invention to a synthetic polymer film or sheet. In the method 1), the antistatic agent for synthetic polymer of the present invention is usually added to 0.0 per 100 parts by weight of the synthetic polymer to be formed into a film or sheet.
The content is 1 to 5 parts by weight, preferably 0.05 to 3 parts by weight. A known method can be applied to the method of incorporating the antistatic agent for synthetic polymer of the present invention into the synthetic polymer, and the method of melt-forming the contained synthetic polymer into a film or a sheet itself. In the method 2), for example, an aqueous solution of the antistatic agent for synthetic polymer of the present invention is prepared and applied to the surface of the synthetic polymer film or sheet by a known method such as a roller touch method or a spray method. Apply. The step of applying, in the manufacturing process of the synthetic polymer film or sheet, a step before stretch orientation immediately after melt extrusion, a step before biaxial stretch orientation after uniaxial stretch orientation, and a step after biaxial stretch orientation However, the step after the uniaxially stretched orientation and before the biaxially stretched orientation is preferred, and in any step of coating, the synthetic polymer film or sheet 1 m ² can be used as the antistatic agent for the synthetic polymer of the present invention.
The coating amount is usually 0.01 to 0.2 g.

The method of applying the antistatic agent for synthetic polymers of the present invention to synthetic fibers is as follows: 1) A method in which the antistatic agent for synthetic polymers of the present invention is incorporated into a synthetic polymer and then made into synthetic fibers. 2) A method of adhering a synthetic fiber containing an antistatic agent for a synthetic polymer of the present invention as an antistatic agent component such as a spinning oil agent or a spinning oil agent can be mentioned.
Is preferred. In the method 1), the synthetic polymer 1 containing the synthetic polymer antistatic agent of the present invention as a synthetic fiber
It is usually contained in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, per 100 parts by weight. Known methods can be applied to the method of incorporating the antistatic agent for synthetic polymers of the present invention into synthetic polymers and the method of using the incorporated synthetic polymers as synthetic fibers. In the method 2), for example, an aqueous solution of a spinning oil agent containing the antistatic agent for synthetic polymer of the present invention is prepared, and then this is subjected to a roller oiling method,
It is attached to the surface of the synthetic fiber by a known method such as a guide oiling method or an immersion oiling method. The attaching step may be any of the spinning step, the drawing step, each step after the drawing, etc., but in any step, the synthetic polymer is used as an antistatic agent for the synthetic polymer of the present invention. It is attached so as to be 0.01 to 5% by weight.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the perfluoroalkylnaphthalene sulfonate represented by Formula 1 and the method for producing the same include the following 1) to 3). 1) Through the following steps A, B, and C, the analysis value of lithium as described later in detail is lithium = 5- (2,2,3,
A method for producing 3-tetrafluoropropyl) -2-naphthalene sulfonate. Step A: 12.8 g of naphthalene and 13.2 g of 2,2,3,3-tetrafluoro-1-propanol are subjected to perfluoroalkylation reaction at a temperature of 90 ° C. using anhydrous aluminum chloride 17.6 g, 5- (2,2,3
A step of producing 3-tetrafluoropropyl) naphthalene. Step B: 5- (2,2,3,3-tetrafluoropropyl) naphthalene 33.6 g produced in Step A and 25%
A step of subjecting 14.2 g of fuming sulfuric acid to a sulfonation reaction at a temperature of 160 ° C. to produce 5- (2,2,3,3-tetrafluoropropyl) -2-naphthalenesulfonic acid. Step C: 5- (2,2,3,3-tetrafluoropropyl) -2-naphthalenesulfonic acid produced in Step B and 11 g of lithium hydroxide are neutralized in an aqueous alcohol solution to obtain lithium = A step of forming 5- (2,2,3,3-tetrafluoropropyl) -2-naphthalene sulfonate.

2) Through the following first step, second step, and third step, the analytical value of sodium as described later in detail = 5- (2,2,3,3,4,4,5,5) -A method for producing octafluoropentyl) -2-naphthalene sulfonate. First step: 12.8 g of naphthalene and 96% sulfuric acid 10.2
a step of subjecting g to a sulfonation reaction at a temperature of 160 ° C. to produce naphthalenesulfonic acid. Second step: naphthalenesulfonic acid produced in the first step and 2,2,3,3,4,4,5,5-octafluoro-
23.2 g of 1-pentanol and 5.6 g of 96% sulfuric acid
And a perfluoroalkylation reaction at a temperature of 100 ° C. to produce 5- (2,2,3,3,4,4,5,5-octafluoropentyl) -2-naphthalenesulfonic acid. Third step: 5- (2,2,3, generated in the second step
3,4,4,5,5-octafluoropentyl) -2-
Naphthalene sulfonic acid and 4.5 g of sodium hydroxide are neutralized in an aqueous alcohol solution to give sodium = 5- (2,2,3,3,4,4,5,5-octafluoropentyl) -2. The step of producing naphthalene sulfonate.

3) Through the following steps A, B, and C, potassium = 5- of the analytical value as described in detail later.
(2,2,3,3,4,4,5,5,6,6,7,7,
8,8,9,9-hexadecylfluorononyl) -2-
A method for producing naphthalene sulfonate. Step A: 12.8 g of naphthalene and 2,2,3,3,4
4,5,5,6,6,7,7,8,8,9,9-hexadecylfluoro-1-nonyl alcohol 43.2 g and 96% sulfuric acid 12.3 g were used at a temperature of 70 ° C. The perfluoroalkylation reaction is carried out with 5- (2,2,3,
3,4,4,5,5,6,6,7,7,8,8,9,9
A step of producing hexadecylfluorononylnaphthalene. Step B: 5- (2,2,3,3, generated in Step A
4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononylnaphthalene 33.6 g and 25
A step of subjecting 14.2 g of% fuming sulfuric acid to a sulfonation reaction at a temperature of 160 ° C. to produce 5- (2,2,3,3-tetrafluoropropyl) -2-naphthalenesulfonic acid. Step C: 5- (2,2,3,3-tetrafluoropropyl) -2-naphthalenesulfonic acid produced in Step B and 27 g of potassium hydroxide are neutralized in an aqueous alcohol solution to give potassium = 5- (2,2,3,3,4,
4,5,5,6,6,7,7,8,8,9,9-hexadecylfluorononyl) -2-naphthalene sulfonate.

Further, as an embodiment of the dispersant of the present invention,
The following 4) are mentioned. 4) A pigment dispersant comprising the perfluoroalkylnaphthalene sulfonate according to any one of 1) to 3) above.

Further, as an embodiment of the antistatic agent for synthetic polymers of the present invention, the following 5) can be mentioned. 5) An antistatic agent for synthetic polymers, which comprises the perfluoroalkylnaphthalene sulfonate of any one of 1) to 3) above.

In order to make the constitution and effect of the present invention more concrete, examples will be given below, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, parts are parts by weight, and% is% by weight.
Means

[0032]

Examples Test Category 1 (Synthesis of perfluoroalkylnaphthalene sulfonate) Perfluoroalkylnaphthalene sulfonate (P-
Synthesis of 1) First, 12.8 g (0.1 mol) of naphthalene and 2,2,3,3-tetrafluoro-1-propanol were placed in a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel. Charge 13.2 g (0.1 mol) and 17.6 g of anhydrous aluminum chloride, and stir at a temperature of 90 ° C. while stirring 5
The perfluoroalkylation reaction was carried out for a period of time. The reaction solution was cooled to 10 ° C. and washed twice with water, then stratified to remove the aqueous layer, anhydrous sodium sulfate was added to the obtained oil layer, and the product was filtered to obtain a brown liquid. 6 g was obtained.
Next, 33.6 g of this product was charged into a four-necked flask similar to the above, the internal solution was kept at 40 ° C. or lower, 14.2 g of 25% fuming sulfuric acid was added, and the temperature was raised to 160 ° C. The sulfonation reaction was carried out under 2 hours. Further, the sulfonation reaction liquid was prepared by separately preparing 11 g of lithium hydroxide.
To a mixed solution of 49 g of water and 73 g of methanol,
The mixture was added dropwise at a temperature of 10 ° C or lower to carry out a neutralization reaction. The neutralization reaction solution was filtered, the solvent was distilled off from the filtrate under reduced pressure, and then the residue was dried in vacuum. The vacuum dried product was subjected to preparative high performance liquid chromatography as described below to fractionate an eluate having a retention time of 7.3 to 8.3. Fraction solution at 40 ℃
The solution was concentrated under reduced pressure below, and further dried under vacuum to obtain a white solid perfluoroalkylnaphthalene sulfonate (P-1). This white solid was analyzed by the following analysis to obtain lithium = 5- (2,2,3,3-tetrafluoropropyl).
It was 2-naphthalene sulfonate.

Preparative high performance liquid chromatography column packing material: Hitachi gel 3053 (trade name of Hitachi, Ltd.) Column diameter: 50 mm Column length: 150 mm Eluent: acetonitrile / 0.05M sodium perchlorate aqueous solution = 10 / 90 (volume ratio) Flow rate: 156 ml / min Column temperature: 40 ° C Measurement wavelength: 254 nm

Analytical method and analytical value Fluorine content by flask combustion method: 23.15% Sulfur content by IPC emission spectroscopy: 9.77% Lithium content by atomic absorption method: 2.11% FT-IR Main peaks (unit: cm ⁻¹ ) (transmittance): 3428 (78%), 3053 (89%), 30
11 (78%), 2960 (79%), 2925 (80)
%), 2853 (79%), 1952 (92%), 18
42 (95%), 1624 (93%), 1595 (93
%), 1506 (87%), 1435 (96%), 13
48 (91%), 1213 (62%), 1146 (70)
%), 1116 (74%), 1084 (73%), 97
6 (93%), 912 (96%), 864 (96%),
823 (89%), 796 (82%), 769 (80
%), 742 (91%), 690 (79%), 619
(80%), 575 (91%), 526 (88%), 4
76 (88%), 445 (89%) UV λmax: 317 nm, 284 nm, 232 nm Chemical shift δ by ¹ H-NMR (unit: pp
m): 8.2, 8.0, 7.9, 7.7, 7.5, 7.
5, 6.4, 4.3 ¹³ C-NMR chemical shift (unit: pp
m): 145.1, 132.5, 131.9, 128.
2,127.3,127.1,126.3,126.
1, 123.9, 123.7, 119.9, 119.
5, 119.2, 116.5, 116.2, 115.
9, 113.3, 112.9, 112.4, 110.
0, 109.6, 109.2, 106.7, 106.
3,105.9,62.2,61.8,61.5

-Perfluoroalkylnaphthalene sulfonates (P-2) to (P-9) and (P-11) to (P
-20) of synthetic perfluoroalkylnaphthalene sulfonate (P-
In the same manner as in 1), perfluoroalkylnaphthalene sulfonates (P-2) to (P-9) and (P-11) to
(P-20) was synthesized.

Synthesis of Perfluoroalkylnaphthalene Sulfonate (P-10) First, 12.8 g (0.1 mol) of naphthalene and 96 were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel. % 10.2 g of sulfuric acid was charged, and the sulfonation reaction was carried out for 1 hour while stirring at a temperature of 160 ° C. Next, the reaction solution is cooled to 30 ° C.
4,5,5-octafluoro-1-pentanol 23.
2 g (0.1 mol) was added, and subsequently, 5.9 g of 96% sulfuric acid was added while maintaining the internal solution at 40 ° C. or lower and stirring, and then the perfluoroalkylation reaction was performed for 12 hours at a temperature heated to 100 ° C. Was done. Then, the reaction solution was added dropwise to a separately prepared mixed solution of 4.5 g of sodium hydroxide, 20 g of water and 30 g of methanol at a temperature of 10 ° C. or lower to carry out a neutralization reaction. The neutralization reaction solution was filtered, the solvent was distilled off from the filtrate under reduced pressure, and then the residue was dried in vacuum. The vacuum dried product was subjected to the same preparative high performance liquid chromatography as described above, and the retention time was 7.3 to 8.3.
Minute eluate was fractionated. The fractionated solution was concentrated under reduced pressure at 40 ° C. or lower and further dried under vacuum to obtain a white solid perfluoroalkylnaphthalene sulfonate (P-10). This white solid was analyzed by the analysis described below to give sodium = 5-
It was (2,2,3,3,4,4,5,5-octafluoropentyl) -2-naphthalene sulfonate.

-Analytical method and analytical value Fluorine content by flask combustion method: 34.21% Sulfur content by IPC emission spectroscopy: 7.22% Sodium content by atomic absorption method: 5.17% FT-IR Main peaks (unit: cm ⁻¹ ) (transmittance): 3378 (68%), 3059 (80%), 30
13 (75%), 2964 (82%), 2928 (83)
%), 2853 (78%), 1949 (90%), 18
42 (92%), 1625 (90%), 1598 (92
%), 1508 (88%), 1435 (95%), 13
49 (91%), 1213 (59%), 1144 (77)
%), 1119 (75%), 1086 (78%), 97
6 (92%), 911 (95%), 864 (93%),
822 (90%), 797 (83%), 770 (82)
%), 742 (90%), 690 (75%), 620
(85%), 570 (90%), 522 (82%), 4
75 (85%), 444 (91%) UV λmax: 317 nm, 284 nm, 229 nm Chemical shift δ by ¹ H-NMR (unit: pp
m): 8.2, 8.0, 7.9, 7.8, 7.5, 7.
5,7.1,4.3 Chemical shift by ¹³ C-NMR (unit: pp
m): 145.0, 133.0, 132.2, 128.
6,127.6,127.6,126.8,126.
6, 124.3, 124.0, 119.0, 118.
6, 116.9, 115.2, 114.8, 114.
5,114.1, 113.7, 113.7, 113.
3,112.2, 111.8, 111.4, 110.
9, 110.6, 110.3, 110.2, 109.
9, 109.8, 109.7, 109.5, 108.
4, 108.0, 107.6, 107.5, 107.
0, 106.7, 106.6, 106.3, 106.
2, 105.0, 104.0, 104.3, 62.3
62.0, 61.7

Synthesis of perfluoroalkylnaphthalene sulfonate (P-21) First, 12.8 g (0.1 mol) of naphthalene and 2 were added to a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel. , 2, 3, 3, 4, 4, 5, 5, 6, 6, 7,
4,8,8,8,9,9-hexadecylfluoro-1-nonyl alcohol 43.2 g (0.1 mol) and 96% sulfuric acid 1
2.3g was charged at 70 ° C or lower, and a sulfonation reaction and a perfluoroalkylation reaction were carried out for 2 hours while stirring at a temperature of 70 ° C. Next, the reaction liquid was cooled to 40 ° C. or lower, 15.2 g of fuming sulfuric acid was added, and the reaction was carried out for 2 hours at a temperature heated to 160 ° C., and then cooled to room temperature. Then, the reaction solution was prepared separately from potassium hydroxide 2
A neutralization reaction was carried out by adding dropwise to a mixed solution of 7 g, 103 g of water and 155 g of methanol at a temperature of 10 ° C. or lower. The neutralization reaction solution was filtered, the solvent was distilled off from the filtrate under reduced pressure, and then the residue was dried in vacuum. The vacuum dried product was subjected to the same preparative high performance liquid chromatography as described above to fractionate an eluate having a retention time of 7.3 to 8.3. The fractionated solution was concentrated under reduced pressure at 40 ° C. or lower and further dried under vacuum to give a white solid of perfluoroalkylnaphthalenesulfonate (P-
21) was obtained. According to the analysis described below, this white solid was potassium = 5- (2,2,3,3,4,4,5,5).
It was 5,6,6,7,7,8,8,9,9-hexadecylfluorononyl) -2-naphthalene sulfonate.

-Analytical method and analytical value Fluorine content by flask combustion method: 46.03% Sulfur content by IPC emission spectroscopy: 4.85% Potassium content by atomic absorption method: 5.92% FT-IR Main peaks (unit: cm ⁻¹ ) (transmittance): 3378 (66%), 3060 (85%), 30
15 (74%), 2960 (89%), 2927 (87)
%), 2852 (89%), 1950 (92%), 18
40 (93%), 1646 (80%), 1598 (89
%), 1508 (86%), 1441 (94%), 13
49 (82%), 1210 (48%), 1144 (67)
%), 1115 (71%), 1071 (66%), 99
6 (78%), 912 (93%), 863 (90%),
824 (86%), 796 (80%), 770 (78
%), 742 (86%), 690 (71%), 618
(76%), 570 (86%), 521 (77%), 4
77 (85%), 441 (89%) UV λmax: 316 nm, 283 nm, 231 nm Chemical shift δ by ¹ H-NMR (unit: pp
m): 8.2, 8.0, 7.9, 7.7, 7.5, 7.
4,7.1,4.3 Chemical shift by ¹³ C-NMR (unit: pp
m): 145.0, 132.7, 132.0, 128.
4,127.4,127.4,126.5,126.
3, 124.1, 123.8, 119.9, 119.
5, 119.1, 117.1, 116.6, 116.
2,115.8,114.9,114.6,114.
4,114.1, 114.0, 113.9, 113.
5, 113.2, 112.8, 112.4, 111.
7, 111.2, 110.8, 110.5, 110.
1, 109.6, 109.3, 108.3, 107.
9, 107.5, 106.9, 106.6, 105.
0, 104.6, 104.1, 62.3, 62.0, 6
Table 1 summarizes the contents of each perfluoroalkylnaphthalene sulfonate synthesized above.

[0040]

[Table 1]

Test Category 2 (evaluation as a dispersant for pigment) Preparation of coating composition Perfluoroalkylnaphthalene sulfonate represented by Formula 1 synthesized in Test Category 1 as a dispersant for pigment, etc. 3
Parts, xylene / butanol = 3/1 (weight ratio) mixed solvent 35 parts, Beckosol EY-3002 (Dainippon Ink and Chemicals Co., Ltd. resin trade name, xylene / butanol mixed solvent 35% contained) 25 parts , Titanium oxide pigment 15
And 150 parts of glass beads (3 mmφ) were mixed in a dispersion container, and then dispersed with a paint conditioner for 2 hours to prepare a mill base. Next, this mill base 87
Part (excluding glass beads), Beckosol 57-
1362 (trade name of resin manufactured by Dainippon Ink and Chemicals,
68 parts of a solvent containing 35%) and Super Beckamine L-117 (commercial name of resin manufactured by Dainippon Ink and Chemicals, Inc., containing 40% xylene / butanol mixed solvent).
Forty-five parts were further dispersed for 5 minutes with a paint conditioner for 5 minutes to prepare a coating composition.

Evaluation of dispersibility To the above coating composition was added a mixed solvent of Solvesso 100 (trade name of Exxon Chemical Co.) / Xylene / butanol / cellosolve acetate = 40/30/20/10 (weight ratio). Then, the viscosity of the Iwata viscosity cup was adjusted to 15 seconds. This was applied on a 10 cm × 10 cm square test panel plate tilted at an angle of 80 °, left in the air for 30 minutes, and then dried by heating at 140 ° C. for 20 minutes to obtain a cured coating film plate. The gloss of the cured coating film of this cured coating plate was measured with a digital conversion gloss meter at 20 ° gloss and evaluated according to the following criteria. The results are summarized in Table 2. A: The 20 degree gloss is 80 or more, and the dispersibility is excellent. ◯: 20 degree gloss is 70 or more and less than 80, and dispersibility is good. B: The 20 degree gloss is less than 70, and the dispersibility is slightly inferior.

Evaluation of antifouling property The above-mentioned cured coating plate was used in 2 parts of carbon black and 90% of upland soil.
Part, and 8 parts of mineral oil, after thoroughly stirring, taken out and wiped with a dry cloth, and the contamination state of the surface of the cured coating film was measured by L value by Minolta CR-200 color difference meter. L value (L ₁ ) of the cured coating plate before the test
And the L value (L ₂ ) of the cured coating film plate after the test were measured, and {(L
₁₋ L ₂ ) / L ₁ } × 100 is calculated from the formula,
The following criteria evaluated. The results are summarized in Table 2. Evaluation criteria ⊚: ΔL is 90 or more, and the antifouling property is excellent. ◯: ΔL is 80 or more and less than 90, and the antifouling property is good. Δ: ΔL is less than 80, and the antifouling property is slightly inferior.

[0044]

[Table 2]

In Table 2, R-1: sodium = 5-pentyl-1-naphthalene sulfonate (hereinafter the same)

Test Category 3 (Evaluation as Antistatic Agent for Synthetic Polymer) Preparation of Sheet 3 parts of perfluoroalkylnaphthalene sulfonate synthesized in Test Category 1 as an antistatic agent for synthetic polymer and polyethylene terephthalate resin 100 And the mixture were put into a Labo Plastomill and kneaded at 280 ° C. for 5 minutes to prepare a synthetic polymer material. This synthetic polymer material was molded by a hot press at 260 ° C. to prepare a sheet having a thickness of 2 mm.

Evaluation of antistatic property The above-mentioned sheet was placed in a constant temperature and humidity chamber of 20 ° C x 45% RH for 2 days.
After humidity control for 4 hours, using a super insulation resistance meter (SM-8210 type manufactured by Toa Denpa Kogyo KK) in the same atmosphere, JIS-K691
The surface resistivity was measured according to 1 and evaluated according to the following criteria. The results are summarized in Table 3. Evaluation Criteria ⊚: The surface resistivity is less than 5 × 10 ¹² Ω, which is excellent. ◯: The surface resistivity is 5 × 10 ¹² Ω or more and less than 5 × 10 ¹³ Ω, which is good. Δ: The surface specific resistance is 5 × 10 ¹³ Ω or more, which is slightly inferior.

Evaluation of antifouling property A 10 cm × 10 cm sample piece was taken from the above sheet and the
Put it in a compound consisting of 2 parts of Bonblack, 90 parts of upland soil and 8 parts of mineral oil, stir it thoroughly, take it out and wipe it off with a dry cloth, and check the contamination state of the sheet surface with a white plate on the back side of the sheet. The L value was measured with a Minolta CR-200 color difference meter. The L value (L ₁ ) of the sheet surface before the test and the L value (L ₂ ) of the sheet surface after the test were measured, and Δ was calculated from the formula of {(L ₁ −L ₂ ) / L ₁ } × 100.
L was determined and evaluated according to the following criteria. The results are summarized in Table 3. Evaluation criteria ⊚: ΔL is 90 or more, and the antifouling property is excellent. ◯: ΔL is 80 or more and less than 90, and the antifouling property is good. Δ: ΔL is less than 80, and the antifouling property is slightly inferior.

[0049]

[Table 3]

[0050]

As is apparent from the above, the present invention described above can provide a novel perfluoroalkylnaphthalene sulfonate which is useful as a dispersant for pigments, an antistatic agent for synthetic polymers and the like, and a method for producing the same. There is an effect.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/42 C08K 5/42 C09K 3/16 108 C09K 3/16 108D // C07B 61/00 300 C07B 61/00 300 F Term (reference) 4D077 AB03 AB14 AB20 AC05 CA03 CA15 DC02X DC04Z DC12Z DC64X DC72X DC72Z 4H006 AA01 AA02 AA03 AB66 AB68 AC23 AC61 BA66 BB14 BB31 BC10 BE03 4H039 CA10 CD10 4J002 AA011 AA021 CF061 EV256FD

Claims (6)

[Claims] 1. A perfluoroalkylnaphthalene sulfonate represented by the following formula 1. [Formula 1] (In Formula 1, n is an integer M of 1 to 7: lithium atom, sodium atom or potassium atom) 2. A method for producing a perfluoroalkylnaphthalene sulfonate represented by the formula 1 according to claim 1, which comprises the following first step, second step and third step. Process for producing alkylnaphthalene sulfonate. First step: a step in which naphthalene and sulfuric acid having a concentration of 90 to 100% are subjected to a sulfonation reaction at a temperature of 140 to 170 ° C. to produce naphthalene sulfonic acid. Second step: The naphthalene sulfonic acid produced in the first step and a perfluoroalkyl alcohol represented by the following formula 2 are subjected to a perfluoroalkylation reaction at a temperature of 0 to 150 ° C. using an acid catalyst to give the following: A step of producing a perfluoroalkylnaphthalenesulfonic acid represented by Formula 3. Third step: a step of neutralizing the perfluoroalkylnaphthalenesulfonic acid produced in the second step and the alkali in an aqueous alcohol solution to produce a perfluoroalkylnaphthalenesulfonate. [Formula 2] [Formula 3] (In Formula 3, n: an integer of 1 to 7) 3. A method for producing a perfluoroalkylnaphthalene sulfonate represented by formula 1 according to claim 1, which comprises the following steps A, B and C: Method for producing acid salt. Step A: naphthalene and a perfluoroalkyl alcohol represented by the formula 2 according to claim 2 by using an acid catalyst
A step of performing a perfluoroalkylation reaction at a temperature of 150 ° C. to produce a perfluoroalkylnaphthalene. Step B: The perfluoroalkylnaphthalene produced in Step A and fuming sulfuric acid are subjected to a sulfonation reaction at a temperature of 140 to 170 ° C. to produce a perfluoroalkylnaphthalenesulfonic acid represented by the formula 3 of claim 2. Process. Step C: a step of neutralizing the perfluoroalkylnaphthalenesulfonic acid produced in Step B and the alkali in an aqueous alcohol solution to produce a perfluoroalkylnaphthalenesulfonate. 4. A dispersant comprising the perfluoroalkylnaphthalene sulfonate according to claim 1. 5. The dispersant according to claim 4, which is a dispersant for pigments. 6. An antistatic agent for synthetic polymers, comprising the perfluoroalkylnaphthalene sulfonate according to claim 1.