JP2893136B2 - Fluorine-containing bisphenol derivative - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a surface modified material having practically sufficient oil solubility and excellent properties such as chemical resistance, weather resistance, stain resistance and flame retardancy. The present invention relates to a novel fluorine-containing bisphenol derivative useful as an agent and the like.

2. Description of the Related Art Bisphenol derivatives, particularly novolak, have excellent chemical resistance and weather resistance, and are frequently used as additives, such as resin raw materials and curing agents for sealing materials. Above all, alkylene oxide adducts of novolak are raw materials for urethane resins, nonionic or anionic surfactants, dispersants for solid fuels such as coal, emulsifiers, dispersing aids for fluororesins in oily paints and inks, etc. It is widely used in various fields.

However, this kind of bisphenol derivative not only has poor antifouling properties and flame-retardant properties, but also has a problem that the oil solubility is insufficient mainly due to the presence of oxyethylene groups.

Problems to be Solved by the Invention The present invention solves such problems and has practically sufficient oil solubility, and is excellent not only in chemical resistance and weather resistance but also in antifouling properties and flame retardancy. The present invention has been made to provide a fluorine-containing bisphenol derivative useful as a surface modifier having the above-mentioned properties.

Means for Solving the Problems That is, the present invention provides a compound represented by the following general formula (I): [In the formula, AO represents an oxyethylene group and / or an oxypropylene group, and at least one of R _{1 to} R ₄ is a fluorinated group C _n F _2n-1 −, C _n F _2n-1 C ₂ H ₄ CO- or (Wherein n is a number from 6 to 9) and the remainder is a hydrogen atom, and R ′ and R ″ may be the same or different and each represents a hydrogen atom, CH ₃ or CX ₃ (wherein , X represents a halogen atom), R represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, m ₁ ,
Or m ₂ represents a number of 0, 1 or 2, and a + b + c
+ D represents a number of 4 to 50].

In the general formula (I), AO represents an oxyethylene group and / or an oxypropylene group, and the number of added moles of AO a
+ B + c + d is 2 to 50, preferably 28 to 40. If the number of added moles is smaller than 2, the surfactant activity cannot be exhibited, and if it is larger than 50, the oil will not be produced due to the presence of oxyethylene groups. Poor solubility.

At least one of R _{1 to} R ₄ represents the following fluorinated group, and the rest represents a hydrogen atom: C _n F _2n-1 , C _n F _2n-1 C ₂ H ₄ CO—, (In the formula, n represents a number of 6 to 9.) R ′ and R ″ may be the same or different and each represent a hydrogen atom, CH ₃ or CX ₃ (X represents a halogen atom).

R represents a hydrogen atom, a halogen atom, preferably a chlorine atom or a bromine atom, or an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or a t-butyl group.

Further, m ₁ or m ₂ indicates a number of 0, 1 or 2.

The method for producing the fluorinated bisphenol derivative represented by the above general formula (I) is not particularly limited, but a preferred production method is the following bisphenol (a) or the bisphenol (a) and the following phenol Novolaks (c) to (f) obtained by subjecting the compounds (b) to formalin condensation under acidic conditions include ethylene oxide and / or
Alternatively, propylene oxide is added according to a conventional method, and at least a part of the active hydrogen at the terminal of the adduct is substituted with the above-mentioned fluorinated group: (Wherein R ′, R ″ and R are as defined above) The addition reaction of the above bisphenols (a) or novolaks (c) to (f) with ethylene oxide and / or propylene oxide is a catalyst. For example, alkali hydroxides (such as sodium and potassium hydroxide), alkali metals (such as sodium and potassium) or alcoholates (such as sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, potassium ethoxide and potassium butoxide) About 14 in the presence of
Perform at 0-160 ° C. The amount of the catalyst used is usually 0.01 to 5% by weight. From the viewpoint of simplicity of post-treatment of the product, it is preferable not to use a solvent, but if desired, an insoluble solvent such as a hydrocarbon solvent, an aromatic solvent or a halogen-containing solvent may be appropriately used. Good.

By adjusting the addition rate of ethylene oxide and / or propylene oxide, specific properties of the target substance, for example, oil-soluble performance and surface activity, can be appropriately adjusted.

The compound represented by the general formula (I) is obtained by reacting the above-mentioned compound having a fluorinated group, for example, a perfluoroolefin or a fluorinated carboxylic acid or a derivative thereof (such as acid chloride) with the adduct obtained by the above addition reaction. Compounds can be prepared. in this case,
By appropriately adjusting the substitution ratio of the active hydrogen at the terminal of the adduct with the fluorine-containing group, the properties of the target substance, such as antifouling property and flame retardancy, can be appropriately adjusted.

Examples of the perfluoroolefin include oligomers of tetrafluoroethylene or hexafluoropropene, for example, compounds represented by the following (g) to (k): The reaction between the above-mentioned perfluoroolefin and the adduct is usually carried out in a solvent in the presence of a catalyst.

As the solvent, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone,
Examples include acetonitrile, diethyl ether, benzene, toluene, xylene, carbon tetrachloride, chlorophore, dichloromethane and the like, and N, N-dimethylformamide and acetonitrile having high dissolving ability are preferable.

As a catalyst, sodium carbonate, potassium carbonate,
Alkaline inorganic salts such as sodium fluoride, potassium fluoride and cesium fluoride and tertiary amines such as trimethylamine, triethylamine, N, N-dimethylaniline and pyridine are exemplified, but potassium carbonate,
Potassium fluoride and triethylamine are particularly preferred. The amount of catalyst used is usually approximately equivalent to the perfluoroolefin.

The reaction temperature depends on the type of reaction components used and the like, but is usually 0 to 40 ° C.

Next, as the fluorinated carboxylic acid and its derivative, the following compounds (l) to (q) are exemplified: In the reaction between the above-mentioned adduct and the fluorinated carboxylic acids (l) to (n), a solvent and / or a catalyst may be used if desired.

Examples of the solvent include aromatic hydrocarbons and halogenated hydrocarbons, and examples of the catalyst include hydrogen chloride gas, sulfuric acid, p-toluenesulfonic acid, and a sulfonic acid type ion exchange resin.

The reaction temperature is usually 140 to 160 ° C when no catalyst is used.
And 110 to 130 ° C. when a catalyst is used.

The adduct and the fluorinated carboxylic acid chloride (o) to
The reaction of (q) may be performed using a solvent and / or a catalyst if desired.

Examples of the solvent in this case include aromatic hydrocarbons, halogenated hydrocarbons, ketones and ethers,
Catalysts include triethylamine, pyridine and N, N-
Dimethylaniline and the like are exemplified.

The reaction temperature is usually from 60 to 150 ° C when no catalyst is used, and from room temperature to 80 ° C when a catalyst is used.

In any of the above-mentioned production methods, in any case, as one of the reaction components or both of the reaction components, if necessary, two or more of them may be used in a single step or in a multi-step manner as appropriate. May be appropriately selected according to the use of the product.

EXAMPLES Hereinafter, the present invention will be described with reference to examples.

Example 1 In an autoclave (1) equipped with a stirring device, a temperature sensor, a cooling device and a pressure gauge, 150 g of bisphenol novolak (polymerization degree: 3 to 5, softening point: 112 ° C), 645 g (14.59 mol) of ethylene oxide and potassium hydroxide 0.5g
And the reaction was carried out at 150 ° C. with stirring for about 8 hours, and the reaction mixture was cooled to room temperature to obtain 795 g of the following compound (1).

 The physical properties of compound (1) are shown in Table 1 below.

Example 2 In a three-necked flask (500 ml) equipped with a stirrer, condenser, thermometer and dropping funnel, 38.76 g of the compound (1) prepared in Example 1, 11.83 g (0.09 mol) of potassium carbonate and 200 ml of acetonitrile were prepared. , And while maintaining the temperature of the contents of the flask at about 5 ° C. or lower using an ice bath, 32.08 g (0.07 mol) of hexafluoropropene trimer is gradually added dropwise with stirring over about 90 minutes. Stir about 15 more
Time continued.

After subjecting the reaction mixture to a filtration treatment and evaporating the solvent,
The residue was dissolved in diethyl ether, allowed to stand overnight, then treated using a short column packed with silica gel, and the solvent was distilled off under reduced pressure to obtain the following compound (2) (yield: 84.78%).

 Table 1 below shows the physical properties of the compound (2).

Example 3 26.09 g of the compound (1) prepared in Example 1 in a three-necked flask (500 ml) equipped with a stirrer, a condenser, a thermometer and a dropping funnel, C ₉ H ₁₇ O.C ₆ H _4. COCl28.15g (0.05mol)
And 150 ml of carbon tetrachloride, 28.15 g (0.05 mol) of triethylamine was gradually added dropwise with stirring over about 30 minutes while maintaining the temperature of the contents of the flask at about 2 ° C. or lower using an ice bath, and the dropping was completed. Thereafter, stirring was continued for about another 24 hours.

After the triethylamine hydrochloride was filtered off from the reaction mixture, the solvent was distilled off from the filtrate to obtain the following compound (3) having the properties shown in Table 1 below (yield: 99.2%).

Example 4 According to the procedure of Example 2, the following compound (4) having the physical properties shown in Table 1 below was obtained (yield: 81.20%).

Effect of the Invention The fluorinated bisphenol derivative according to the present invention has multifunctional properties, that is, properties such as chemical resistance, weather resistance, antifouling property, flame retardancy, lipophilicity and hydrophilicity, and these various properties are Since it can be adjusted by appropriately selecting the type and content of the fluorinated group and the alkylene oxide, for example, a nonionic surfactant, a solid dispersant, an emulsifier, an antistatic agent, an anti-mist agent, a polyol of a urethane resin It can be used as a component, an alcohol-soluble paint, an oil-soluble paint, a coating agent, a leveling agent, or a raw material thereof.

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): [In the formula, AO represents an oxyethylene group and / or an oxypropylene group, and at least one of R _{1 to} R ₄ is a fluorinated group C _n F _2n-1 −, C _n F _2n-1 C ₂ H ₄ CO- or (Wherein n is a number from 6 to 9) and the remainder is a hydrogen atom, and R ′ and R ″ may be the same or different and each represents a hydrogen atom, CH ₃ or CX ₃ (wherein , X is indicates a halogen atom), R represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms, m ₁ or m ₂ is a number of 0, 1 or 2, also a + b + c +
d represents a number of 2 to 50].