JPS63277219A - Fluorine-containing phenol resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled resin excellent in the surface characteristics such as water and oil-repelling properties, antifouling property and friction properties and suitable also in a water and oil-repelling agent, etc., by reacting a phenol resin with a specific perfluoroalkene in the presence of a basic catalyst. CONSTITUTION:A phenol resin is reacted with a perfluoroalkene expressed by the formula Rf-F {Rf is perfluoroalkenyl expressed by formula I [R1-R3 are perfluoroalkyl expressed by the formula -CnF2n+1 (n is 1-6)]} in the presence of a basic catalyst (preferably tertiary amine such as trimethylamine) to provide the aimed resin replacing a phenolic OH group of the phenol resin with a fluorine-containing ether substituent group. As the perfluoroalkene, e.g. hexapropene oligomer expressed by formula II is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention has properties such as water and oil repellency, non-stick properties (antifouling properties), chemical resistance, heat resistance, and low friction and abrasion resistance (sliding properties). The present invention relates to a functional fluorine-containing phenolic resin having various properties and a method for producing the same.

Conventional technology Phenolic resin has excellent electrical insulation, mechanical strength, dimensional stability, and heat resistance, so it is used as a molding material for electrical parts and automobile parts, and for laminated products such as industrial plates and pipes. It has not only been widely used as a material for shell molds, wood processing adhesives, etc., but also as a material for brakes, clutches, etc. due to its good self-lubricating properties.

However, phenolic resins have the disadvantage of poor water resistance due to the presence of phenolic hydroxyl groups (especially they tend to swell or dissolve in alkaline aqueous solutions), and compared to fluororesins, which have superior surface properties. The problem is that it has poor sliding properties.

Problems to be solved by the invention The present invention improves these drawbacks of phenolic resins,
This was done in order to provide a functional phenolic resin having excellent properties such as water and oil repellency, stain resistance, chemical resistance, heat resistance, and sliding properties.

A means for solving the problems, that is, the present invention, provides that at least a part of the phenolic -OH of the phenolic resin is a fluorine-containing ether substituent -0RfC, where Rf is the following formula: Fluoroalkyl group -C
n, F (n indicates a number from 1 to 6)) is 2n
+1 represents a perfluoroalkenyl group] As the base resin of the fluorine-containing phenolic resin according to the present invention, there are known phenolic resins such as phenol, cresol,
Resol-type or novolak-type phenolic resins obtained by addition-condensation reaction of phenols such as xylenol and resorcin and aldehydes such as formaldehyde, acetaldebide and furfural, and modified resins thereof may be used as appropriate. From this point of view, a particulate phenolic resin having an average particle size of 500 microns or less is useful for manufacturing and utilization reasons described below.

A feature of the fluorine-containing phenolic resin according to the present invention is that at least a portion of the phenolic hydroxyl groups of the above-mentioned phenolic resin are substituted with a fluorine-containing ether group -0Rf. In this case, Rf represents a perfluoroalkenyl group represented by the above general formula, and R1, R2 and R3 each represent a perfluoroalkyl group -CnFZn+1
(n represents a number of 1-10, preferably 1-6).

Preferred Navarfluoroalkenyl groups are hexafluoropropene oligomer residues and/or tetrafluoroethylene oligomer residues, for example fat-tel
Examples include those expressed as: (at
tbl (c) (d)el The substitution rate of the phenolic hydroxyl group by the fluorine-containing ether group -0Rf may be appropriately selected depending on the intended use of the resin, and is not particularly limited. Properties such as water and oil repellency, antifouling properties, sliding properties, and heat resistance can be adjusted as appropriate.

The basic structure of the fluorine-containing phenolic resin according to the present invention is that phenols as main chain components are crosslinked by methylene bonds or dimethylene ether bonds, and at least a part of the phenolic hydroxyl groups are fluorine-containing ether substituents -o
Although this is a structure substituted by Rf, methylol groups remain in various proportions depending on the type of resin, degree of crosslinking, etc.

Generally, the higher the residual rate of methylol groups, the higher the solubility and reactivity with respect to solvents will be an uncured resin, and conversely, the lower the residual rate with respect to solvents, the lower the solubility and reactivity with respect to solvents will be a curable resin.

The method for preparing the fluorine-containing phenolic resin according to the present invention is not particularly limited, but a preferred method is to prepare a phenol resin and a perfluoroalkene Rf-
This is a method of reacting p (in the formula, R (has the same meaning as above).

As the phenolic resin, the above-mentioned resins may be used as appropriate, but in general, if the degree of curing is too high, the substitution rate of phenolic hydroxyl groups by fluorine-containing ether-substituted 1-oR ( It is necessary to select a resin that maintains swelling properties and does not cause adhesion, aggregation, deformation, etc.

However, depending on the application, it may be necessary to increase the fluorination rate of the phenolic resin, which has a considerably high degree of curing, as much as possible. In such cases, it is effective to use a finely divided phenolic resin having an average particle size of 500 microns or less as described above.

Suitable perfluoroalkenes Rf''F are hexapropene oligomers and/or tetrafluoroethylene oligomers, such as those represented by the following formulas) to (j): tf) t
g) thl filCF3 tj) The above phenolic resin and perfluoroalkene R (-F
The reaction ratio may be appropriately selected depending on the type of reaction components, desired fluorination rate, etc., and is not particularly limited.

Examples of basic catalysts include tertiary amines such as trimethylamine and triethylamine, inorganic basic salts such as sodium carbonate and potassium carbonate, pyridine, and N,N-dimethylaniline. Amines are preferred.

The amount of the basic catalyst used is also not particularly limited, but it is generally used in an amount equivalent to the reaction amount.

The above reaction is usually carried out in an organic solvent.

Organic solvents include acetonitrile, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone,
In addition to polar solvents such as diglyme and triglyme, examples include henzene, toluene, xylene, ether, tetrahydrofuran, and acetone. These organic solvents may be appropriately selected depending on the type of reaction components, but when using a phenol resin with low swelling or solubility, a polar solvent such as dimethylformamide or dimethyl sulfoxide is selected.

The reaction temperature also depends on the type of reaction components, and is usually 0 to 100°C, although it is not particularly limited.

The fluorine-containing phenolic resin obtained by the above reaction has an infrared absorption spectrum of 1100 to 1300 C1.
Since it exhibits a characteristic absorption derived from C-F stretching vibration near 1, it can be easily identified based on this.

Although the fluorine-containing phenolic resin according to the present invention may be used as a single polymer, it usually contains various additives, such as curing agents (for example, ammonia having an amine bond, hexamethylenetetramine, etc.), modifiers (for example, rosin, Nisder gum, drying oil, synthetic rubber, etc.), fillers (e.g. linters, wood flour, paper, asbestos, whiskers, glass fibers, metal fibers, synthetic fibers such as polyamide, polyester 8 and polyvinyl chloride, alumina, mica, talc, mold release) It is used as a composition containing an appropriate amount of additives, molybdenum disulfide, etc.), a plasticizer, a coloring agent, a diluent, a flame-retardant additive, etc.

Effects of the Invention The fluorine-containing phenolic resin according to the present invention not only has excellent surface properties in terms of water and oil repellency, stain resistance, and sliding properties, but also has physical properties such as hardness, heat resistance, and weather resistance. Since it has been improved, it can be used for a variety of purposes, including various surface treatment agents such as water and oil repellents, anti-adhesive agents, and sliding agents, in addition to the conventional uses of phenolic resins.

In particular, the fine particulate fluorine-containing phenolic resin of the present invention exhibits excellent functions as a solid lubricant, so it can be blended with plastics, rubber, paints, coating agents, lubricating oils, etc. rubber,
High-slip paints or coating agents (eg, magnetic tape coating agents, etc.) and highly lubricating greases can be obtained.

Further, the above-mentioned excellent properties of the fluorine-containing phenolic resin according to the present invention can be freely adjusted by appropriately selecting the fluorination rate and the type of perfluoroalkenyl depending on the individual purpose.

Furthermore, the fluorine-containing phenolic resin according to the present invention can be provided at a lower cost than conventional high-performance resins such as polyoxybenzoic acid.

Hereinafter, the present invention will be explained by examples.

Example 1 D M F30tx in a three-hole flask (100 In/) equipped with a dropping funnel, thermometer, stirrer and reflux condenser
lf, 5.3 g of microspherical phenol resin and 5.1 g of triethylamine were dissolved therein with stirring, and 15.0 g of hexafluoropropene dimer was added into the solution with stirring.
was gradually added dropwise, and the reaction was carried out for 3 hours.

The reaction mixture was neutralized using diluted hydrochloric acid, and then thoroughly washed with water to obtain 18.0 g of a solid product.

Confirmation of the product is 3500 in the infrared absorption spectrum.
Decrease in CH stretching vibration absorption near C11” and 1100
-1300 cm (This was done by generating CF stretching vibration absorption near q (substitution rate of pheno-/l/A OH with fluorine-containing groups: about 5 to 20%).

Example 2 A reaction was carried out in the same manner as in Example 1 except that hardened microspherical phenol resin was used as the phenolic resin and the resin was stirred and dispersed in DMF to obtain a fluorine-containing phenolic resin in the form of spherical particles.

The product was confirmed in the same manner as in Example 1 (substitution rate of phenolic -OH with fluorine-containing groups in a relatively thin surface layer: about 5 to 20%).

The angle of repose of this product was about the same as that of the raw resin.

Also, put this product in a beaker (layer thickness: about 2 cm)
), water was poured into this and the device was kept at 25° C. for more than one day, but no water penetrated into the packed particle bed at all.

Furthermore, the granular fluorine-containing phenolic resin obtained in this example was uniformly kneaded at a ratio of 10% by weight to nylon 6 BRL 1030 for injection molding using a twin-screw kneading extruder with a diameter of 45 mm. The sliding characteristics of test piece A, which was made from a mixed material using an injection molding device, were investigated. The results are shown in Table-1.

For comparison, test pieces B or C made by blending 10% by weight of raw material phenol resin or ultra-high molecular weight polyethylene with nylon 6, and test piece D made from only nylon 6 were examined in the same manner for sliding properties. The results are shown in Table-1.

Table-1 (1) Measured using a precious wood type abrasion tester (mate material: steel S-45G, circumferential speed: 20ts/sec
, surface pressure 2 1.7 KP/c11) As is clear from the results in Table 1, the surface properties of the particulate fluorine-containing phenolic resin according to the present invention and the sliding properties of molded products containing the resin were significantly improved. ing.

Claims (1)

[Claims] 1. At least a part of the phenolic -OH of the phenolic resin is a fluorine-containing ether substituent -ORf [In the formula, Rf is the following formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ {In the formula, R_1 to R_3 each represent a perfluoroalkyl group -CnF_2_n_+_1 (n represents a number from 1 to 6)]
A fluorine-containing phenolic resin characterized by being substituted with. 2. The fluorine-containing phenolic resin according to item 1, wherein Rf is a hexafluoropropene oligomer residue and/or a tetrafluoroethylene oligomer residue. 3. Hexafluoropropene oligomer residue or tetrafluoroethylene oligomer residue has the following formulas (a) to (e)
): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼(d) ▲There are numerical formulas, chemical formulas, tables, etc.▼(e) The fluorine-containing phenolic resin according to item 2, which is a perfluoroalkenyl group represented by the following. 4. The fluorine-containing phenolic resin according to item 1, wherein the phenolic resin is a particulate phenolic resin having an average particle size of 500 microns or less. 5. Phenol resin and perfluoroalkene Rf-F in the presence of a basic catalyst [In the formula, Rf is the following formula: ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ {In the formula, R_1 to R_3 are each a perfluoroalkyl group -CnF_2_n_+_1 (n represents a number from 1 to 6)} represents a perfluoroalkenyl group]
A fluorine-containing phenolic resin in which at least a part of the phenolic -OH of the phenolic resin is substituted with a fluorine-containing ether substituent -ORf (wherein Rf has the same meaning as above). Production method. 6. The manufacturing method according to item 5, wherein the perfluoroalkene is a hexafluoropropene oligomer and/or a tetrafluoroethylene oligomer. 7. Hexafluoropropene oligomer or tetrafluoroethylene oligomer has the following formulas (f) to (j): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (f) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (g) ▲ Mathematical formulas , chemical formulas, tables, etc.▼(h) ▲Mathematical formulas, chemical formulas, tables, etc.▼(i) ▲Mathematical formulas, chemical formulas, tables, etc.▼(j) Production method. 8. The manufacturing method according to item 5, wherein the phenol resin is a particulate phenol resin with an average particle size of 500 microns or less.