JPS62129310A - Fluorine-containing polyester - Google Patents

Abstract

PURPOSE:The titled polyester, obtained by copolymerizing fluorine-containing isophthalic acid with terephthalic acid, having a high polymerization degree, good hue and improved heat resistance and moldability and useful as water and oil repellent fibers, films, etc. CONSTITUTION:A fluorine-containing polyester obtained by reacting 5- hydroxyisophthalic acid or an ester thereof with a perfluoroalkyl halide to form a fluorine-containing isophthalic acid to be structural units expressed by formula I (Rf is 1-20C perfluoroalkyl: n is an integer 0-6), incorporating the resultant fluorine-containing isophthalic acid (A) with terephthalic acid (B) to be structural units expressed by formula II so as to give 1/99-20/80 molar ratio of the components (A) to (B) and polycondensing the resultant mixture with a glycol (C) to be structural units expressed by formula III (R is 2-4C polymethylene or 1,4-cyclohexylenedimethylene).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fluorine-containing polyester useful as molded articles such as fibers and films having 1Ω water and T8 oil properties.

(Prior Art) Organic fluorine compounds, especially compounds having a perfluoroalkyl group, have a low critical interfacial tension.

A stain-resistant fiber that exhibits remarkable water and oil repellency.

It is widely used as a surface treatment agent for obtaining paper, leather, etc.

For example, as a method of imparting stain resistance to polyester fibers, the fibers are treated with an organic fluorine compound selected from high molecular compounds such as fluoroalkyl esters of polyacrylic acid and low molecular compounds such as fluorine-containing urethane compounds. has been adopted. However, with this surface treatment method, the adhesion between the fiber and the organic fluorine compound film is insufficient.

Along with poor cleaning resistance and abrasion resistance.

There was a problem that the process became complicated.

As a method to solve these problems, there is a method of introducing an organic fluorine compound into the fiber by a blending method or a copolymerization method. For example, Textile Research
Journal, 47, 551-561 (1977) discloses a method of melt-mixing polyester and an aromatic fluorine compound, but this fluorine compound inherently has poor affinity with polyester, and Although it has the advantage that the fluorine compound with low melt viscosity forms a surface layer of the fiber and exhibits good 1Ω water and oil repellency when melt-mixed with the fiber, there are problems with the uniformity of the mixture and durability. . In addition, when introducing organic fluorine compounds into polyester fibers by copolymerization, conventional methods produce polymers with a high degree of polymerization and one color tone that can withstand high temperatures of 250°C or higher during single polycondensation or melt spinning. However, it was difficult to obtain fibers with good strength and color tone.

(Problems to be Solved by the Invention) The present invention aims to provide a fluorine-containing polyester that has excellent heat resistance and moldability and is useful as molded products such as water- and oil-repellent fibers and films. .

(Means for Solving the Problems) The present invention achieves the above nine objects, and the gist thereof is as follows.

It consists of structural units represented by the following formulas (1) to (III), and the molar ratio of structural units (I) to (II) is 1/99 to
2°/80, a random copolyester in which the total number of moles of the structural unit (1) and (former) are substantially equal to the number of moles of the structural unit (I), and the intrinsic viscosity is 0.3 to 1.5. A fluorine-containing polyester.

[n is an integer of 0 to 6, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms, and R is a polymethylene group or 1,4-cyclohexylene dimethylene group having 2 to 4 carbon atoms. ] In the present invention, the hardness and viscosity of polyester are defined as:

Measurements were taken at 25°C using an equal weight mixture of phenol and tetrachloroethane as a solvent.

The fluorine-containing polyester of the present invention is a random copolyester obtained by copolymerizing a fluorine-containing isophthalic acid component with a polyester mainly composed of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, or poly-1,4-cyclohexylene dimethylene terephthalate. be.

Such a polyester of the present invention can be produced by a conventional method batchwise or continuously.

That is, when producing a polyester by obtaining a monomer or oligomer by an esterification reaction between terephthalic acid and glycol or a transesterification reaction between a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and glycol, and polycondensing the monomer or oligomer, It can be produced by adding and copolymerizing a monomer or oligomer of fluorine-containing isophthalic acid or its lower alkyl ester or fluorine-containing isophthalic acid component and glycol.

At this time, as a catalyst for transesterification reactions and polycondensation reactions,
Zinc, cobalt, manganese, calcium.

Metal compounds such as titanium, antimony, germanium, etc., and stabilizers such as phosphoric acid, phosphorous acid, phosphonic acid, or esters thereof are added as necessary.

Polycondensation reactions are usually carried out in a molten state.

The prepolymer obtained by melt polycondensation reaction can also be subjected to solid phase polycondensation reaction.

In the present invention, the fluorine-containing isophthalic acid compound forming the structural unit (I) can be obtained by reacting 5-hydroxyisophthalic acid or its ester with a compound of Rf (CHz) n X CX is halogen.

Various limitations on the polyester of the present invention were made in consideration of fiber and film forming ability, heat resistance during melting, performance required of the resulting fibers and films, etc., but there are particularly important factors. is the number of carbon atoms in Rf, the structural unit (1
) and (II) and the intrinsic viscosity of the polyester. When Rf has about 4 to 15 carbon atoms, it is water repellent!
8 oil effect is the best.

The larger the molar ratio of structural units (I) and (II), the more 1a water.

The oil repellent effect is great, but in terms of m fibers and film forming ability, it is 20%
/80 or less, preferably 2/9
8-15/85 is good. The intrinsic viscosity is 0 in terms of fiber and film forming ability and physical properties of the resulting fibers and films.
．． It needs to be in the range of 3 to 1.5.

A range of 0.4 to 1.2 is particularly preferred.

The polyester of the present invention is composed of structural units (1) to (1), but a mixture of two or more types of glycols may be used as the glycol forming the structural unit (I), or a mixture of two or more glycols may be used, or the effect of one polyester of the present invention may be improved. Other copolymerization components may be introduced as long as they do not impair the properties. Specific examples of other copolymerized components include diethylene glycol, polyethylene glycol, neopentyl glycol, adipic acid, sebacic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, naphthalene dicarboxylic acid, and other bifunctional compounds; trimethylolpropane; Examples include trifunctional or higher functional compounds such as pentaerythritol and trimellitic acid.

(Examples) Next, the present invention will be specifically explained using examples and application examples. (“Parts” indicate parts by weight.) Examples 1 to 3 and Comparative Example 1 5-n-perfluorononanyl isophthalic acid (FI
P) and an esterified product of terephthalic acid and ethylene glycol (number average degree of polymerization 4) (TPAG) were charged into a reactor equipped with a stirrer in the proportions shown in Table 1, and 0.03 part of antimony dioxide was added as a single polycondensation catalyst. It was added in the form of a 1% ethylene glycol solution and heated at 250°C and normal pressure under a nitrogen stream.
After reacting for an hour, the temperature was raised to 280°C and the pressure was gradually reduced to reach 0.1 wllg in 30 minutes.
A time polycondensation reaction was performed.

The obtained polyester had a good color tone without any two-coloring.

The characteristic values of this polyester are shown in Table 1.

In Table 1, the characteristic values were determined as follows.

■ The melting point was determined by differential thermal analysis at a heating rate of 10°C/mi.
It was calculated using n.

■ The DEC (diethylene glycol) content was determined by decomposing polyester with methanol at 150°C and analyzing it by gas chromatography.
The proportion of the EC component is shown in mol%.

■F (fluorine) content was determined by elemental analysis.

■ Ratio of structural unit (1) and (I[) [(I)/(I
I)) was calculated from the F content.

(2) γC (critical surface tension) was calculated from the contact angle of water droplets formed on a polyester sheet.

In addition, the infrared absorption spectrum of polyester was
The results measured with let's FT-IR7199 are shown in the first to
Shown in Figure 3. [Figure 1 shows the spectrum of the polyester of Example 1, Figure 2 shows the spectrum of the polyester (polyethylene terephthalate) of Comparative Example 1, and Figure 3 shows the difference spectrum between the polyesters of Example 1 and Comparative Example 1. ] Table 1 Application Examples The polyester chips obtained in Example 2 were melted at 280"c using an extruder type melt spinning machine, and spun through a nozzle with a diameter of 0.3 mm to 1,200 m/m.
The yarn was wound at a speed of 1.5 in. and stretched 2.8 times at 90'c to obtain a drawn yarn of 75d/24f.

The obtained drawn yarn has a strength of 3.2 g/d and an elongation of 29.7%.
in.

Thread reeling properties were good.

This drawn yarn was woven into taffeta at a weave density of 100 yarns/2.54 cm in both warp and warp, and after scouring, it was dyed in a dye bath containing a blue disperse dye at 130° C. for 1 hour.

After drying the dyed cloth, water droplets are dropped on the cloth.

Even after 10 minutes, no water droplets penetrated the fabric.

(With ordinary polyethylene terephthalate taffeta, water droplets penetrate the fabric after 10 seconds.) (Effects of the Invention) According to the present invention, fibers with good water repellency and T8 oiliness,
A fluorine-containing polyester with excellent heat resistance and moldability that is useful as a molded product such as a film is provided.

[Brief explanation of drawings]

Figures 1 to 3 show the infrared absorption spectra of polyester, and Figure 1 is the spectrum of the polyester of Example 1;
Figure 2 is the spectrum of polyester (polyethylene terephthalate) of Comparative Example 1, Figure 3 is the spectrum of Example 1 and Comparative Example 1.
shows the difference spectrum of polyester.

Claims (1)

[Claims] (1) Consists of structural units represented by the following formulas (I) to (III), with a molar ratio of structural units (I) and (II) of 1/9
9 to 20/80, the total number of moles of structural units (I) and (II) is substantially equal to the number of moles of structural unit (III), and the intrinsic viscosity is 0.3 to 1.
．． 5, a fluorine-containing polyester. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) [n is an integer from 0 to 6, Rf is A perfluoroalkyl group having 1 to 20 carbon atoms, R represents a polymethylene group having 2 to 4 carbon atoms or a 1,4-cyclohexylene dimethylene group. ]