JP2592915B2 - Fluorine-containing polyether polyester - Google Patents

Description

The present invention has characteristics such as excellent water repellency, oil repellency and low friction and wear resistance as well as excellent durability, heat resistance, elasticity and adhesion. It relates to a fluorine-containing polyether polyester.

2. Description of the Related Art Polyether polyesters are excellent in durability, heat resistance, elasticity, adhesion, etc., and have been conventionally used, for example, thermoplastic polyester-based elastic resins, polyester resin adhesives, antistatic agents, coating agents, etc. However, since the properties such as water repellency, oil repellency, lubricity and slidability are insufficient or lacking, improvement is demanded.

Problems to be Solved by the Invention The present invention meets such demands and provides a polyether having properties such as oil repellency and low friction and abrasion resistance in addition to inherent properties such as excellent durability and adhesion. This was done to provide polyester.

Means for Solving the Problems That is, the present invention provides a compound represented by the general formula [I]: (In the formula, Rf represents a perfluorohexenyl group C ₆ F ₁₁ or a perfluorononenyl group C ₉ F ₁₇ , R represents a hydrogen atom or a methyl group, n represents a number of 2 to 140, and m represents 2 or more. The present invention relates to a fluorine-containing polyether polyester represented by the following formula:

In the general formula [I], Rf is a perfluorohexenyl group C ₆ F ₁₁ or a perfluorononenyl group C ₉ F ₁₇ , for example, derived from a dimer or trimer of hexafluoropropene C ₃ F ₆ . Examples of such perfluoroalkenyl groups include those represented by the following structural formula: In the formula [I], R represents a hydrogen atom or a methyl group, and n represents a number of 2 to 140. That is, polyethylene glycols of the formula [I] in CH ₂ CH (R) O _n is divalent residues which are derived from diethylene glycol or polyethylene glycol and / or dipropylene glycol or polypropylene glycol, preferably having an average molecular weight of 300 to 4000 And / or divalent residues derived from polypropylene glycol.

In addition, this kind of divalent residue may be composed of two or more kinds of residues having different molecular weights.

Further, in the formula [I], m is a number of 2 or more, preferably 5 to 150.

The method for producing the fluorinated polyether polyester represented by the general formula [I] is not particularly limited, but the general formula [II]: (In the formula, Rf represents a perfluorohexenyl group C ₆ F ₁₁ or a perfluorononenyl group C ₉ F ₁₇ , and X represents a hydroxyl group, a chlorine atom, a methoxy group or an ethoxy group.) Alkenyl) oxyisophthalic acid or a derivative thereof and general formula [III]: (Wherein, R represents a hydrogen atom or a methyl group, and n is 2
Shows the number of ~ 140. ) Is preferable.

5- (Perfluoroalkenyl) oxyisophthalic acid or a derivative thereof represented by the general formula [II] can be obtained, for example, by adding a dimer or trimer of hexafluoropropene C ₃ F _{6 to} 5-hydroxyisophthalic acid or a derivative thereof in the presence of a basic catalyst. It can be prepared by reacting below.

When X is a hydroxyl group in the formula [II],
When 5- (perfluorohexenyloxy) isophthalic acid or 5- (perfluorononenyloxy) isophthalic acid is reacted with the diol represented by the formula [III], usually, equimolar amounts of both components are converted to zinc acetate and acetic acid. The reaction is performed in the presence of a catalyst such as calcium or antimony trioxide.

The amount of the catalyst used is 0.005 to 0.1% by weight, preferably 0.01 to
0.05% by weight.

This reaction is carried out under reduced pressure in an atmosphere of an inert gas (eg, N ₂ gas, CO ₂ gas, etc.) at 100 to 350 ° C., preferably 150 ° C.
Perform at ~ 320 ° C for about 5-15 hours.

Further, when X is a chlorine atom in the formula [II],
When 5- (perfluorohexenyloxy) isophthalic acid chloride or 5- (perfluorononenyloxy) isophthalic acid chloride is reacted with a diol represented by the formula [III], usually, equimolar amounts of both components are used. 0-300
C., preferably at 0 to 200.degree. C. under normal pressure or reduced pressure for about 1 to 25 hours. In this case, if desired, an inert solvent such as carbon tetrachloride or benzene may be used as a reaction solvent, or a basic catalyst such as pyridine or triethylamine may be used as appropriate. Furthermore, the formula [II]
Wherein X is a methoxy group or an ethoxy group, that is, a transesterification reaction in which 5- (perfluorohexenyloxy) isophthalic acid ester or 5- (perfluorononenyloxy) isophthalic acid is reacted with a diol represented by the formula [III] In the case of, equimolar amounts of both components are combined in the presence of a catalyst such as zinc acetate, calcium acetate, antimony acetate or titanium oxide in an inert gas (eg,
N ₂ gas, CO ₂ gas, etc.)
The reaction is carried out at -350 ° C, preferably 150-320 ° C, for about 5-15 hours.

The amount of the catalyst used is usually 0.005 to 0.1% by weight, preferably
It is 0.01 to 0.05% by weight.

In the above components, two or more kinds of polyethylene glycols and / or polypropylene glycols having different molecular weights may be appropriately used as the diol component.

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

Example 1 64.9 g of 5- (perfluorononenyloxy) isophthalic acid chloride and 10.6 g of diethylene glycol were placed in a reaction vessel equipped with a stirrer, a thermometer, and a N ₂ gas introduction tube.
After heating for 2 hours at 100-120 ° C under normal pressure in a N ₂ gas stream, heating for 2 hours at 150-160 ° C under reduced pressure (20-30mmHg), and 3 hours at 150-170 ° C at 2mmHg Fluorine-containing polyether polyester I by heat reaction
74.8 g of a was obtained.

 Table 1 shows the physical properties of the polymer Ia.

Example 2 20 g of polyethylene glycol (average molecular weight: 400), 16 g of pyridine and 50 ml of carbon tetrachloride were placed in a reaction vessel equipped with a stirrer, a thermometer, and a condenser. On the other hand, 32.4 g of 5- (perfluorononenyloxy) isophthalic acid chloride
Was dissolved in 150 ml of carbon tetrachloride, and the solution was added dropwise to the above mixture. In this case, the reaction was cooled using an ice-water bath.

After completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours, and further reacted at 50 to 60 ° C. for 5 hours.

The reaction mixture was subjected to a filtration treatment, and the filtrate was subjected to an evaporation treatment under reduced pressure to remove the solvent, thereby obtaining 45.2 g of a fluorinated polyether polyester Ib.

 Table 1 shows the physical properties of the polymer Ib.

Example 3 5- (Perfluorononenyloxy) isophthalic acid was placed in a reaction vessel equipped with a stirrer, a thermometer, and a N ₂ gas inlet tube.
18.4 g polyethylene glycol (average molecular weight: 2000) 60
g, 0.1 g of zinc acetate and 20 ml of m-xylene, and stirred under heating at 140 to 150 ° C. for 20 hours in a N ₂ gas stream at normal pressure, and then 0.1 g of antimony trioxide was added, and 20 to 30 mm
After heating and stirring at 150 to 170 ° C. for 10 hours under Hg, 77.3 g of a fluorine-containing polyether polyester Ic was further heated and stirred at 170 to 190 ° C. at 2 to 3 mmHg for 5 hours. Obtained.

 Table 1 shows the physical properties of the polymer Ic.

Example 4 According to the same reaction procedure as in Example 1, a fluorinated polyether polyester Id was obtained using 5- (perfluorononenyloxy) isophthalic acid chloride and polyethylene glycol (average molecular weight: 6000) as starting materials. .

 Table 1 shows the physical properties of the polymer Id.

Effect of the Invention Since the fluorine-containing polyether polyester according to the present invention has properties such as excellent water and oil repellency, low friction and abrasion resistance, durability, heat resistance, elasticity and adhesion, a high performance polyester elastomer, Lubricants, release agents, finishing agents for modifying various substrates (films, fibers, paper, plastics, rubber, etc.), antistatic agents, polymer surface modifiers (eg, lubricity and repellency to film surfaces) It is useful as an agent for imparting water / fouling resistance, antifogging / antifog properties and antistatic properties, and an agent for imparting sliding properties to the surface of a magnetic recording medium.

Continuation of front page (72) Inventor Fujito Nemoto 1-1, Oikecho, Kosai-cho, Koka-gun, Shiga Prefecture Neos Co., Ltd. (56) References JP-A-62-206019

Claims (2)

(57) [Claims] 1. A compound of the general formula [I]: (In the formula, Rf represents a perfluorohexenyl group C ₆ F ₁₁ or a perfluorononenyl group C ₉ F ₁₇ , R represents a hydrogen atom or a methyl group, n represents a number of 2 to 140, and m represents 2 or more. A fluorine-containing polyether polyester represented by the following formula: 2. The general formula [II]: (In the formula, Rf represents a perfluorohexenyl group C ₆ F ₁₁ or a perfluorononenyl group C ₉ F ₁₇ , and X represents a hydroxyl group, a chlorine atom, a methoxy group or an ethoxy group.) Alkenyl) oxyisophthalic acid or a derivative thereof and general formula [III]: (Wherein, R represents a hydrogen atom or a methyl group, and n is 2
Shows the number of ~ 140. A method for producing a fluorine-containing polyether polyester represented by the general formula [I], characterized by reacting a diol represented by the following formula: