JPS6050788B2 - Cyanuric chloride derivatives of hexafluoroepoxypropane oligomers and their uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel compounds cyanuric chloride derivatives of hexafluoroepocycyproban oligomers and their uses.

That is, the gist of the present invention is the general formula: (wherein Y is Cl or N(CH2CH2OH)2,
n represents 0, 1, 2 or 3.

) and its uses.

In order to produce the compound (1) of the present invention, an anilide of hexafluoroepoxypropane oligomer is synthesized by reacting a hexafluoroepoxypropane oligomer with nitroaniline, as represented by the following formula, and the nitro group is replaced with iron. After reducing the amino group with a metal such as tin, zinc, or aluminum and an acid such as hydrochloric acid, the compound may be reacted with cyanuric chloride, or the compound obtained in this step may be further reacted with diethanolamine. Invention compound (1) binds to cellulose etc. in the presence of a base at room temperature in the case of the dichlorotriazine derivative (1a) and at 80 to 100°C in the case of the monochlorotriazine derivative (Ib), and becomes water repellent. , oil repellent. It is useful as a fiber treatment agent for textile products because it imparts properties such as durability and stain resistance.

For example, in order to make cotton fabric water and oil repellent using the compound (1) of the present invention, at least 1 equivalent of a base such as sodium hydroxide or aqueous ammonia, preferably 1 to 2 equivalents, should be added per mole of the compound (1) of the present invention. The compound (1) of the present invention may be dissolved in a water-soluble solvent such as acetone or acetonitrile, and a cotton cloth or the like may be immersed in this solution.

The immersion time may be about 3 hours to 2 hours. Many copolymers of polyfluoroacrylate or methacrylate have been developed as water and oil repellents, but many are unsatisfactory in terms of washing resistance and dry cleaning resistance.

On the other hand, those containing the compound of the present invention as an active ingredient impart durable water and oil repellency especially to fibers containing active hydrogen such as cotton, wool, nylon, vinylon and the like. Furthermore, the compound of the present invention has the advantage that its production is relatively simple and easy, as described above.
The present invention will be specifically described below with reference to Examples.

Example 1 The following amount of tetrameric hexafluoroepoxypropane oligomer was added dropwise to the following acetrinitrile solution at room temperature and stirred for 2 hours: Tetrameric hexafluoroepoxypropane oligomer
10j; C (15.1 mm01) acetonitrile solution m-nitroaniline 2.1y (15.1 mm
01) Triethylamine 1.89 (18mm01
) 20ml of acetonitrile, then
The entire amount was poured into water, extracted with ether, and dried to obtain 10.5 g of anilide.

This was placed in a mixture consisting of the following and refluxed for 4 hours: iron powder 3y water
5 mL Concentrated hydrochloric acid 0.5 mL Ethanol 50 mL After distributing iron powder from house to house, ethanol was distilled off under reduced pressure and extracted with ether.

After drying over magnesium sulfate, the ether was removed under reduced pressure to yield 8.4y of the crude amine. This was purified using a silica gel column to obtain amine 7.6y. Then, the following amount of amine was added dropwise to the following acetone solution of cyanuric chloride at 0-5 °C, and further NaHCO3O. A 1 molar aqueous solution was added dropwise and stirred for 1 hour while maintaining the pH at 7: amine.
6.3y (5.4mm01) Acetone solution cyanuric chloride 1. Leap j (8.4mm01)
Next, 20ml of acetone was poured into ice water, and the mixture was overdried to obtain a crude cyanuric chloride derivative (melting point: 105-1095.2q).

This was further recrystallized with toluene and the melting point was 112-114.
4.7y of cyanuric chloride derivative (yield 61%) was obtained. Examples 2 to 4 In the same manner as in Example 1, cyanuric chloride derivatives of dimer, trimer, and pentameric hexafluoroepoxypropane oligomers were synthesized.

The yield, melting point, 19F' NMR chemical shift value, and elemental analysis results of the cyanuric chloride derivatives obtained in Examples 1 to 4 are shown in the following table.

Examples 5 to 8 Using each of the derivatives obtained in Examples 1 to 4, cotton cloth was treated to be water and oil repellent.

Two treatment solutions with the following formulation were prepared for each derivative.

Derivative 3 parts by weight IN-N
aOH aqueous solution 1 equivalent of acetone per 1 mole of derivative
10 parts of cotton cloth was immersed in 2 parts by weight of each treatment solution at room temperature for 1 hour, and one part was washed with water.
One was washed with acetone and each was air-dried.

The water repellency and oil repellency are shown in the table below. The water repellency was evaluated according to AATCC test method 22-1971, and the oil repellency was evaluated using AATCC test method 22-1971. Law (Textile Research Jou
rrlal,? , 320 (1960)).

In addition, stain resistance is evaluated by measuring the change in the contact angle with water over time, and the contact angle with water is large immediately after treatment and decreases with the passage of contact time. It is easy to repel and has excellent properties that make it easy to remove stains when washing in water (for example, 1
A surface layer was obtained and further recrystallized from toluene.

3V01.17N0.1124 (1979)).

Example 9 The cyanuric chloride derivative of the pentameric hexafluoroepoxypropane oligomer obtained in Example 4 was dissolved in acetone and stirred for 1 hour while adding diethanolamine dropwise at 30 to 40°C.

The usage amount of each is as follows. Cyanuric chloride derivative 2.13f (2rT1m0I) acetone
30mL diethanolamine
0.21q (2rT1m01) Then, the entire amount was poured into water, and the precipitated solid was dried in an Oki sieve to obtain a diethanolamine derivative of a cyanuric chloride derivative of a crude pentameric hexafluoroepoxypropane oligomer of 1.9 da.
It was further recrystallized with toluene.

Example 10 Yield, melting point, and di-7nolamine derivative of the cyanuric chloride derivative of tetrameric hexafluoroepoxypropane oligomer from the cyanuric chloride 2☆null derivative obtained in Example 1 in the same manner as in Example 9. The chemical shift values of NMR and 1HNMR are shown in the table below.
;8.

Example 11 3 parts by weight of the diethanolamine derivatives obtained in Examples 9 and 10 were each dissolved in 20 parts by volume of acetone, and 100 parts by weight of cotton cloth was dipped in each, wrung out, and immediately before the acetone dried. It was placed in a NaOH aqueous solution of PHll, immersed at 100°C for 3 hours, washed with water, and air-dried.

Water- and oil-repellency and stain-repellent properties of each cotton fabric were evaluated based on compositions such as cotton fabric and water, and cotton fabric and oil (volume of n-heptane: volume of n-heptane = 70:30, composition showing a judgment value of 80 by the method). ) by measuring the contact angle.

The results are shown in the table below. With oil, no change in the contact angle was observed immediately after the drops were allowed to stand and after one drop, but with water, the contact angle was observed to decrease over time, indicating antifouling properties. Example 12 In Example 11, the contact angles of water and oil were measured for a cotton cloth that was air-dried without being treated with the NaOH aqueous solution of PHll.

However, the contact angle of oil is as follows for the sample of Example 9
The sample of Example 10 was tested using a mixture of 5 volumes of n-heptane and 50 volumes of n-heptane (100 judgment value composition of 0M method). The following results are shown in the table below. From this result, it is understood that although no change in oil repellency is observed over time, water repellency decreases over time, indicating that stain resistance is observed.

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, Y is Cl or N (CH_2CH_2OH)
_2, n represents 0, 1, 2 or 3. ) Cyanuric chloride derivative of hexafluoroepoxypropane oligomer. 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, Y is Cl or N (CH_2CH_2OH)
_2, n represents 0, 1, 2 or 3. ) A fiber treatment agent containing a cyanuric chloride derivative of hexafluoroepoxypropane oligomer as an active ingredient.