JPS6078930A - Production of fluorine-containing dicarboxylic acid and its derivative - Google Patents

Abstract

PURPOSE:To produce the titled compound, easily, by reacting a perfluoroalkyl iodide with a fluorine-contaning unsaturated dicarboxylic acid ester, and if necessary, subjecting the ester group of the reaction product to a proper chemical treatment such as hydrolysis, etc. CONSTITUTION:The objective compound of formula II can be produced by reacting the compound of formula RfI (Rf is 2-21C perfluoroalkyl) with the compound of formula I (R1 and R2 are 1-5C alkyl; m is 0, 1 or 2). If necessary, the ester group of the reaction product is subjected to a proper chemical modification process such as hydrolysis, eater exchange, or conversion to metal salt, ammonium salt, etc. to obtain another objective compound of formula III (M1 and M2 are alkali metal, ammonium, H or 1-5C alkyl). The reduction of the compound gives the compound of formula IV. The compounds of formula II- formula IV are useful as the raw material of polyurethane or polyester, or a modifier to impart the polyurethane or polyester with water and oil repellency.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a fluorine-containing dicarboxylic acid and its derivatives, and more particularly to a method for producing a dicarboxylic acid having a perfluoroalumyl group, its esters and salts, and diols derived therefrom. Regarding.

Fluorine-containing dicarboxylic acids are produced by reacting malonic acid diester with perfluoroalkyl groups and substitutions (for example, 5, U.S. Pat. No. 3,578,70).
No. 1, No. 3,639,438).

As a result of repeated research to develop a simpler method for producing fluorine-containing dicarboxylic acids and their derivatives, the present inventors have discovered that fluorine-containing dicarboxylic acids and their derivatives can be produced by reacting perfluoroalkyl iodides with fluorine-containing unsaturated dicarboxylic acid esters. The present invention was completed by discovering that a fluorine-containing dicarboxylic acid can be produced by obtaining a dicarboxylic acid ester and hydrolyzing it. RE represents a perfluoroalkyl group having 2 to 21 carbon atoms.] A compound represented by [wherein R1 and R2 are each an alkyl group having 1 to 5 carbon atoms, and m is 0.1 or The reaction results in the formula: [In the formula, R1, R2, Rf and m have the same meanings as above.

[In the formula: , Rf i and m have the same meanings as above. Ml and M
2 represents alkali gold@1 ammonium hydrogen or an alkyl group having 1 to 5 carbon atoms, respectively. ] A process for producing a fluorine-containing dicarboxylic acid and a derivative thereof, characterized by obtaining a compound represented by [→], and a chemical kettle [■]. τ Formula: [In the formula, Rf and m have the same meanings as above. ] A method for producing a fluorine-containing diol is provided.

The reaction between compound [1) and compound CI) may be performed by reacting them themselves or in the presence of a solvent. Solvents include methyl ethyl ketone, butyl acetate, tetrahydrofuran, diethyl nitrile; Peroxides such as carbonates are used.

Reaction temperature 4; t, 10-150°C1Special 4C30-10
00C is preferred.

There are no particular restrictions on the reaction pressure, and normal pressure is usually employed.

Hydrolysis, transesterification, metal salting, etc. of compound [111] can be carried out in a conventional manner (this yields free carboxylic acids, various esters and salts).

The corresponding diol can be obtained by reducing the compound [■] or [IV].

As the reducing agent, for example, lithium aluminum hydride, sodium borohydride, lithium borohydride, hydrogen and platinum oxide, hydrogen and palladium, sodium and alcohol, etc. are preferably used.

The reaction is carried out in a solvent such as diethyl erthyl, digtyl ether, tetrahydrofuran, dioxane, N-methylmorpholine, methanol, etc. and at a temperature of 5 to 1 o'clock, preferably at the reflux temperature of the solvent.

The reaction pressure is usually normal pressure, but when hydrogen is used as the reducing agent, a pressure of from normal pressure to 150 atmospheres is used.

The amount of reducing agent to be used is the stoichiometric amount or 10 times the stoichiometric amount; for example, when lithium aluminum hydride is used, at least 1 mol should be added per 1 mol of the raw material compound.

Like this? Oxidation of the diol [V,] produced by 4J yields an iodine-free carboxylic acid. Oxidation may be carried out by a conventional method using potassium dichromate or potassium permanganate.

The fluorine-containing dicarboxylic acid and fluorine-containing diol obtained by the present invention have a small number (at least two incyanate groups of 1
Polyurethane can be produced by reacting with incyanate contained in the molecule. Moreover, any of them can be used as a monomer for producing polyester.

Furthermore, these fluorine-containing dicarboxylic acids and diols can be added as modifiers to ordinary polyurethane, polyester, nylon, etc., and used to impart water and oil repellency.

Next, examples and application examples will be shown to collectively explain the present invention.

Example 1 Into a Li four-jewel flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 0.11 mi of allyl malonic acid diethyl ester, (CF3) 2CFIO, 13 mi, and 5 g of azobisin butyronitrile were charged, and the flask was heated. After the internal air was sufficiently replaced with nitrogen, the temperature was raised to 70°C with stirring, and the reaction was carried out at the same temperature for 3 hours. Then heated at 100 °C under reduced pressure to remove excess (CF3), 2CF I
was removed. Pale yellow liquid (CF3) as residue 2C
F CH2CLI I C1-12CH (COOC2H
5) Obtained 241g.

Example 2 7.5 g of lithium aluminum hydride was charged into a 2-hole flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and after purging the inner space of the flask with nitrogen, 5001°C of diethyl ether was added from the dropping funnel. added. Then,
A solution of 0.1 mA of the ester obtained in Example 1 in diethyl ether 200111 was added from the dropping funnel over 2 hours, and the mixture was further heated under reflux for 15 minutes. After cooling, dilute hydrochloric acid 1
The organic phase was separated from the aqueous phase, and the organic phase was distilled to give (('', to +1'),, Cp /C[7
, l)n ("J-1/Cl-1^('1rJ'lo
The boiling point was 144°C/20
nun HgONMR2δ(PI)Ill)-2,5(
broad), 1.65-1.80 (bl'Oa(
3.77 (doubteL), 415 (I
nfoad).

Example 3 (CF3) A pale yellow viscous liquid C6F13C was prepared in the same manner as in Example 1 except that C6F131 was used instead of 2CFIO.
H2CHICII2C1l (C; 00C2115)
I got 2.

Example 4 The same procedure as Example 2 was repeated except for using the ester obtained in Example 3 to prepare C6F 13 (CI-12) 3CH (CH201~
1) Obtained 2. Boiling point 163°C/20 Iran l
-1g0 Melting point 41°C0 Example 5 Pale yellow viscous liquid C81'17 was prepared in the same manner as in Example 1 except that C6F131 was used instead of (CF3)2CFIO.
CI-12, C1-11cI-12cH (COOC2H
5) Got 2.

Example 6 CRF17 (CI19) qCH (C1-1901-
1) 9 fa-'at, -*B, f5-190°G
/ 20 mmHg0 melting point 81°C6NMR.

δ (PPm) −2,5 (broad), 1.65
= 1.80. (broad), 3.77 (do
ublet), 4.15 (broad).

Application example Tolylene diisocyanate 1 River O no C6F14 (CH2) 3 CH(CH20H)2
0.1 m'J was added, and the reaction was allowed to proceed at room temperature with stirring until the mixture became homogeneous. Then, hexanediol 0.9
After m071 was processed and stirred and mixed, it was cast on a glass plate and reacted at room temperature for 24 hours. The reaction product was a strong thinner film. The contact angles of water and n--7 xane on this film were measured and found to be 126° and 7f, respectively.

Patent applicant Daikin Industries Co., Ltd. Agent Patent attorney Qingbai Bo (2 others) Procedural amendment (shu) April 17, 1981 Patent application No. 18'7563 No. 2, name of invention Fluorine-containing dicarboxylic Process for producing acids and their derivatives 3, relationship with the case of the person making the amendment Patent applicant address 1-1112-39, Shigakawa, IL-ku, Osaka-shi, Osaka υ
1vi steep hill name (285) Guijuun”: work 1゛1
:Shikikai Representative Yu ID Minoru 4, Agent 7, amend the following part in the detailed explanation of the invention column of the statement of contents of the amendment.

(1) On page 4, line 8, "iodization" was corrected to "iodination."

(2) At the end of page 6, lines 8-7, "valeronitrile" has been corrected to "azobisvaleronitrile."

(3) In line 6 at the end of page 6, [t-butyl percarbonate] was corrected to "L-butyl peroxyin butyrate."

that's all

Claims (1)

[Claims] 1. A compound represented by the formula: fl is reacted with a compound represented by the formula: to obtain a compound represented by the formula: If necessary, the ester moiety is hydrolyzed, transesterified, A method for producing fluorine-containing dicarboxylic acids and derivatives thereof, characterized in that a compound represented by the formula is obtained by subjecting it to an appropriate chemical transformation such as metal salt or ammonium salt [wherein R1 and R2 each represent the number of carbon atoms] 1 to 5 alkyl group; Rf is a perfluoroalkyl group having 2 to 21 carbon atoms; Ml and M2 each represent an alkali metal, ammonium, hydrogen, or an alkyl group having 1 to 5 carbon atoms; m is 0.1 or 2; . ]. 2. A compound represented by the formula: Rfl is reacted with a compound represented by the formula: to obtain a compound represented by the formula: If necessary, the ester moiety is subjected to appropriate treatment such as hydrolysis, transesterification, metal salt or ammonium salt conversion, etc. A method for producing a fluorine-containing diol, characterized by subjecting it to chemical conversion to obtain a compound represented by the formula: and further reducing this to obtain a compound represented by the formula: [wherein R1 and 2] are each an alkyl group having 1 to 5 carbon atoms, Rf is a perfluoroalkyl group having 2 to 21 carbon atoms, Ml and M2 are each an alkali metal, ammonium, hydrogen, or an alkyl group having 1 to 5 carbon atoms.
, 1 or 2. ].