JPS60123442A - Fluorine-containing carboxylic acid or its ester and production thereof - Google Patents

Abstract

NEW MATERIAL:A fluorine-containing carboxylic acid or ester thereof expressed by the formula [A is expressed by formula I or II (Rf is 1-11C fluoroalkyl; Rf' is CF3; R3 is CH3 or CF3; n is 1, 2 or 3); R1 and R2 are H, F, RfCH=CH or Rf'R3C=CH, at least one of R1 and R2 is expressed by formula III (R4 is H or lower alkyl; m is an integer 4-11)]. EXAMPLE:The compound expressed by formula IV. USE:An emulsion paint and a raw material for coating materials, plastics, fibers, surfactants or emulsifying agents having antistaining properties, etc. PREPARATION:A cyclic ketone expressed by formula V is reacted with hydrogen peroxide to form a cyclic ketone peroxide, which is then reacted with a monomer expressed by the formula RfCH=CH2 or Rf'R3C=CH2 (R3 is CH3) in the presence of a ferrous salt to afford the aimed compound expressed by the formula R1-A-R2 (R2 is CH3).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new and useful fluorine-containing carboxylic acid or its ester, and its L-ary system.

The fluorine-containing carboxylic acid or ester thereof of the present invention has the general formula % () [wherein A is +CR (HCH2+n or +CR'fR
8CHw+n CR (is a fluoroalkyl group at carbon DI-11, R7 is a fluoromethyl group, R8 is a methyl group, n
is an integer from 1 to 8), R1 and R2 are the same or different hydrogen atoms, fluorine atoms, n4ooc(-cu2+m (
R4 is a hydrogen atom or a lower alkyl group, m is an integer of 4 to 11), R(CH=CH- or R(RBC=CH(R(,
R' (and R8 are the same as above), provided that R1 and R
Both of 2 are a hydrogen atom, a fluorine atom, a compound represented by RfCH±CH- or R (not RBC=CH-).

The lower alkyl group herein refers to an alkyl group having 1 to 4 carbon atoms.

The fluorine-containing carboxylic acid or its ester represented by the above general formula CI) is a novel compound discovered by the present inventor for the first time and which has not been described in any literature. Compounds obtained by oxidizing a telomer of tetrafluoroethylene and methanol are conventionally known as fluorine-containing carboxylic acids, but these compounds are simply compounds in which a carboxyl group is directly bonded to a fluorine-containing functional group. . In contrast, the compound of the present invention has a long chain methylene group or a vinyl group and a long chain methylene group between the fluorine-containing group and the carboxyl group, and has a chemical structure different from that of conventionally known compounds. It is a new compound with different characteristics.

The compounds of the present invention are used for various purposes, and for example, synthetic resin prepolymers (e.g., epoxy resin prepolymers, urethane resin prepolymers, etc.) synthesized by adding the compounds of the present invention can be used as emulsions with extremely excellent emulsifying properties. It can become.

The synthetic resin prepolymer can be used, for example, as an emulsion paint. In addition, the use of the synthetic resin prepolymer as a resin component results in paints, plastics,
Fiber Sl can impart antifouling properties.

The compounds of the present invention are useful as synthetic raw materials for paints, plastics, fibers, and the like. The compounds of the present invention are also useful as synthetic raw materials for surfactants, emulsifiers, and the like.

Representative compounds of the present invention represented by the above general formula [I] are listed in Table 1 below.

Table 1 1, (CF3)2CH(CH2)6COOCH82,
H(C(CF3)2CH2)2(CII2)5COOC
HB8, H(C(CFs)2cHz)B(CII2)5
coocHs4, (CF a')z C=CH(C(
CFg)2cHs+h(CH2)scOOcHs5, (
CF a )2C=cu(C(CFa)2GHz)B
(CH2)5COOCR116, (CFa)2cH(C
Hz)acOOH7,H(C(CFB)2CH2)z(
CIH2)scOOI(8,H(C(CF8)2CH2
)a(CI(,)5COOH9,C5F1rcH2Cc
H2)6coocx(B10, CB117CH=CH
(C112)6COOCII812, (CFs)2CF
CF2CF2cIl(CH2)acOOcH318,(
CFs)2CF(CF2CF2)2CII(CI(2)
6COOCHB14, cpBcp2cF2cp2 (c)
t2)7coocn315, CF2CF2(CF,C
F2)2(CH2)7COOCHgThe "L compound" of the present invention is a cyclic ketone represented by the general formula [wherein m represents a divisor of 4 to 11] and hydrogen peroxide,
Then, the generated cyclic ketone peroxides have the general formula % () [wherein Rf represents a fluoroalkyl group having 1 to 11 carbon atoms] or the general formula (% formula %) [wherein R'f represents a fluoro alkyl group] methyl group, R3 represents a methyl group] is produced by reacting a monomer represented by the following in the presence of a ferrous salt.

In the reaction between the cyclic ketone represented by the general formula [■] and hydrogen peroxide, the ratio of the two to be used is not particularly limited and may be appropriately selected within a wide range, but the latter is usually 0% of the former. It is preferable to use about .5 to 2 times the mole, preferably about the same mole. Specific examples of the cyclic ketone of general formula [11] include cyclopentanone, cyclooctanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone. Also, as hydrogen peroxide, it is usually about 80~
It is used in the form of an aqueous solution of 70% concentration.

The reaction is preferably carried out in a suitable solvent. Solvent rJ includes methanol, ethanol, inpropatol, n-
Examples include lower alcohols such as butanol and tert-butanol, acetonitrile, benzene, and dimethylpolamide. Among these, it is preferable to use methanol, especially anhydrous methanol. The reaction is preferably carried out in the presence of an acid catalyst, thereby increasing the yield of Jm-like ketone peroxides by 11 iJ.

As the acid catalyst, for example, sulfuric acid, hydrochloric acid, iron acid such as phosphorus 119, etc. can be used, preferably sulfuric acid. The amount of such an acid catalyst to be used is usually 0.05 to 0.5 mol lk per 1 mol of the 11-shaped ketone of general formula [11]. The reaction is generally carried out at -70 to 50°C, preferably -10 to 20'C, and usually completes in about 5 to 60 minutes. Cyclic ketone peroxides are produced.

In the present invention, female ketone peroxides may be isolated from the above reaction product and used for the next reaction, or the above reaction product may be used as it is or after being concentrated and used for the next reaction. good.

The above general formula ([
As the monomer represented by 1) or (III'),
CFBCF2C11=CH2 CF2CF2(CF2CF2)2CH=CH2CF3C
F2(CF2CF2)4CH=CH2(CFs)
2CFC■=CH2 (CF8)2CF(CF2CF2)8CH=CH2(c
pa) gcp(cp2cpg)4cu=cn2C;FB
CCHs) C=CH2 (cFa) 2C=CI(2, etc.).

Since the above-mentioned monomer has a vinyl group bonded to a fluorine-containing group, it has an affinity for a cyclic ketone in the reaction with the monomer, and therefore has high reactivity, and is excellent as an industrial method for synthesizing cyclic ketones.

In the reaction between a cyclic ketone peroxide and a monomer of the front general formula (R1) or (III'), the proportion of the two used is not particularly limited and may be appropriately selected within a wide range, but the former is usually used. On the other hand, it is preferable to use the latter in an equimolar to 8-fold molar amount, preferably 2 to 4 times the molar amount. The reaction is preferably carried out in a suitable solvent. As the solvent, the same solvent as used in the reaction between the cyclic ketone and hydrogen peroxide can be used. The reaction is carried out in the presence of ferrous salts. Examples of ferrous salts include ferrous sulfate, ferrous chloride, and ferrous ammonium sulfate. The amount of such ferrous salt is usually 0.1 to 2 mol, preferably 0.8 to 1.0 mol, per mol of cyclic ketone peroxide.
It is preferable to use 2 moles. To describe a preferred embodiment of the reaction, for example, a predetermined amount of general formula (Ill) or (Il
l') monomer is added to the solvent, generally 170 to 50
℃, preferably at a temperature of -10 to -20℃ to form a suspension solution, then add a predetermined amount of ferrous salt to the suspension solution, and then add the cyclic ketone peroxides produced above under stirring. It is best to drip it. This reaction is +;,y′
, (, +, The yield of the target product can be further improved if the reaction is carried out in a gas stream.The reaction time of the reaction is generally 1
~7 hours.

The cyclic ketone peroxides produced when a cyclic ketone and hydrogen peroxide are reacted in a lower alcohol are lower alkoxy cyclic ketone peroxides, and therefore cannot be used in the subsequent reaction of the cyclic ketone peroxides with a fluorine-containing olefin. The compound of the present invention represented by the general formula CI) is mainly produced in the form of an ester (that is, in the general formula CI, R8 represents a lower alkyl group). Therefore, among the compounds of the general formula CI), a compound in the form of a carboxylic acid (ie, a compound in which R8 represents a hydrogen atom in the general formula [I]) is synthesized by hydrolyzing the above-mentioned ester by a conventional method. Furthermore, the cyclic ketone peroxides produced when the raw ketone and hydrogen peroxide are reacted in a solvent other than a lower alcohol are cyclic ketone peroxides, and therefore the subsequent cyclic ketone peroxides and fluorine-containing olefins In the reaction with, the compound of the present invention represented by the general formula (I) is produced in the form of a carboxylic acid (-basic acid or dibasic acid). Therefore, among the compounds of the general formula [I], the ester compound can be synthesized by esterifying the above carboxylic acid by a conventional method.

The thus produced compound of the present invention can be easily isolated and purified by conventionally known separation means such as solvent extraction and distillation. Further, excess fluorine-containing olefin, solvent, etc. present in the reaction product are recovered by a simple distillation operation and reused.

The present invention will be further explained below with reference to Examples.

Example 1 A sharp tip in a reactor with a stirrer! [600 ml of water and methanol! , cooled to 0-5℃, and added 120g of cyclohexanone (
1.22 mol), 8.02 mol of concentrated sulfuric acid, and 112 OF 85% aqueous hydrogen peroxide were added, and stirring was continued for 60 minutes to produce methoxycyclohexanone peroxide. Anhydrous methanol 600 ml was added to a separate stirred reactor through nitrogen gas.
ml! and cooled to -i 0 'C, and then added 840y of ferrous sulfate (heptahydrate) and 880y of hexafluoroinbutene.
00y (1.88 mol) is added to make a suspension J solution. This suspension was cooled to -10'C, and the above methoxycyclohexanone peroxide-containing solution was added dropwise to the stopper while stirring. After stirring for 2 hours, the reaction solution was naturally heated to room temperature. After distilling off methanol, organic layer (upper layer)
Separate. Pickling, washing with water and drying yields pale yellow oily crude product 4
I got 107.

This crude ester was evaporated to obtain the next volume.

(1) Boiling point 50-72℃/15 mmHg28.7
m5.8Wt9g) Main component Methyl caproate (211F) Point 102℃/15mm1 (y96.8
! 7(2B, 5Wt96) (CFa)zcH(CII2)6COOCII3MY
294Mass: m/e=294(M+)59 (
C00CIIB) 111FMR (CDCI 8): δ 1.2-2.0 (10H, m, -〇H2-)
2.80 (2)1. t, J=7.811z, -CH3
CO-)2.86 (IH, α-ael+, J=6.0
,8.41Hz, \CH- / 8.65 (811,8,0CH3) "F NMR (CDC1s') Et [, τFAδ
-11,8 (OF, d, J=8.9IIZ, CFa)
(3) Boiling point 185-145℃ / 15 m1i11 (
946,07 (11,2wt%) D H(C(OF8)2CH2)2(CH2)6 CO
CooCRll 458 25.11 MaSa: m/e=458(M”) 427(M+-
0CIIn) 59 (COOCHs) 2) H(C(cp3)2CHz)B(cn2)5co
ocng MW a 2212.8fI Mass: m/e= 622 (M+) 59 (COO
CIIll) 8)(OF8)2c=cH((CFB)2CCH2)(
CI(2)6COOCHgNW 456 0. IF Mass: m/e=456(M+)425(M
+-0CI(3) 59 (C00CII 3) 4) (OF8)2C=CI((CFg)2CC112
)2(CI12)5COOCJ[sMW 620 7.
89 Mass: m/e= 620 (M+) 589 (M+
-0CR! + ) 5g (coocuB) (41 still residual boiling point 145℃ / 15 mmu9 or more J: 244F (
59,5Wl)1) (CFB)2C=C11(C(C
F3I)zcH2)(CII2)6COOCH3MW4
56 8.87 2) (OF8)2C=CH((CFg)2CCH2)
2(CHg)6COO(j138 isomer MW 620
58.07 8) H-((CFB)2CC112)B(CH2)6
COOC! IB2 isomer MW 622 17.89 64, OF Example 2 250 ml of methanol was stirred in a reactor equipped with a stirrer! and cooled to 0-5℃ and added 68g of cyclohexanone (0.6℃).
4% /l/ ), DI & acid 15F! and 85% peroxide water X68F were added and stirring was continued for 60 minutes to produce methoxycyclohexanone peroxide. 250 ml of anhydrous methanol in a separate stirred reactor through nitrogen gas!
and cooled to 10°C, and then added sulfuric acid (7-hydrate salt).
142Si and C5Fx7C) I=CII2140F(
0.81 mol) to form a cloudy solution.

This suspension was cooled to 0 to 5°C, and the upper part of the methoxycyclohexanone peroxide-containing liquor was gradually added dropwise with stirring. After finishing dropping 2I1. After continuing stirring, the reaction solution was naturally warmed to room temperature. After distilling off the methanol, the lower phase was washed with 1-11fL acid, washed with water and dried to obtain crude product 2007 as a pale yellow oil. As a result of gas chromatography analysis, this product contained the following components.

+l+ Low boiling point component 10.2! i' +2I C3F17CH=CH260,6P+a+ C
3F17CII2(CH2)6COOCH.

MW 576 20. +11 Mass: m/e= 576 (M+)5 9 (C
00CHB ) +41 C3F17CH=CH(CH2)5COOCH
.

MW 574 80°87 M88! l:m/e== 574(M+)5 9 (C
00CR,) +51 CHllooC(CII2)5CH(C11g
)6COOCH3C3F1? MW 704 57.6P Example 8 The same procedure as in Example 1 was carried out except that hexafluoroinbutene was used in place of cyclohexanone, and as a result, the data shown in the table below was obtained.

(Above) Procedural amendment (Self-restraint March 5, 1985 Patent Application No. 231029 2, Title of invention Fluorine-containing carbodiic acid or its ester, Okamura Oil Co., Ltd. (and 1 other person) 4. Agent: Tsuru Hill, 10sawa, Hirano-cho 2, Higashi-ku, Osaka Tel: 06-203
-0941 (6521) Patent Attorney Eiji Saegusa 5, Date of Amendment Order ``Spontaneous 6, Number of inventions increasing due to amendment Contents of correction! The scope of claims is amended as shown in the attached sheet.

2. "Methyl group" on page 4, line 6 of the specification is corrected to "methyl group or fluoromethyl group."

3 Ming! Ill, page 5, lines 7 to 8, the ``melamine group'' is corrected to ``methylene group.''

4. The statements in Table 1 from page 6, line 8 to page 7, line 6 of the specification are corrected as follows.

[Table 1 1H(CF3)2C(CH2)6COOCH32H((
CF3)2CC//2)2(CH2)5COOCII3
3H((CF3)2CCH2)3(CH2)5COOC
R34(CF3), 2C-cH((CF3)2CCH2
)2(CH2)5COOCH35(CF3)2CshiH(
(CF3)2CCH2)3(CH2)5COOCI36
R(CF3)2C(CR2)6COOI! 7H ((CF
3)2CCH2)2(CR2)5COOH8H((CF
3)2CCR2)3(CH2)5COOH9C8F,7
CH2(CH2)6COOCII.

IQ C8F,,CH-cH(C112)5COOCI
I.

lllCH300C(CH2)5CH-(CF12)6
COOcH3C8F□7 12F (CF3)2CCF2CF2CII (C112)
6COOCI1313F(CF3)2C(CF2CF2
)2CIl(CH2)6COOCH314CF3CF2
CF2CF2(CH2)7COOCII315 CF3
CF2(CF2CF2)2(C112)7COOCH3
16H(CF3)2C(Cll2)6COOC//3
”5 The formulas in Mei II+, page 10, lines 6 to 13 are corrected as follows.

J CF3CF2Cl1111111 C//2CF3
CF2 (CF2CF2)2CH-CI12CF3CF2
(CF2CF2), C11-C112F(CF3)2
CCIf w C112F(CF3)2C(CF2CF
2) 3CH-cH2F(CF3)2C(CF2CF2)
14CH-CH2Cノ13(CH3)C, Cll2 (CF,)2Cm C112J 6 "Front line" in the first line of page 11 of the specification is corrected to "the above."

7. "Passion" on page 14, line 16 of the specification is corrected to "fish oil."

8 Replace “(CF3)2CH(CH2)6COOCII3” on page 15, line 4 of the specification with “
H(CF3)2C(CH2)6COOCH3”.

9 "a-st door J" on page 15, line 12 of the specification "d"
-1τ1 house.''

! 0 “Ett, τFA” on page 115, line 15 of the specification [
Correct Ext, T'FAJ.

+1 Formula 1 on page 16, line 1 of the specification % 12 Formula “H(C(CF3)2CH2)3(CH2)5C00C on page 16, line 8 of the specification
H3'' to 1'-//((CF3)2CC112)3(C
'112) Corrected as 5COOCH3J.

13 Formula on page 17, line 11 in specification 9 1 set% I am corrected.

14 The formulas in the first and second lines of page 18 of the specification are corrected as follows.

(above) Claims ■ General formula % formula % [In the formula, A is CRfHCH2'tn or -fCR
f'R3C11,->, , (Rf ha carbon number 1-11
+7) fluoroalkyl group, Rf' is a fluoromethyl group, an integer of ~3), R□ and R2 are the same or different hydrogen atoms, fluorine atoms, R400CfCII2T (Ra
is a hydrogen atom or a lower alkyl group, m is an integer of 4 to 11), Rfctt, ctt- or I? fl R3C-C1
1-(Rf, I?f/ and R3 are the same as above), provided that R1 and R2 are both hydrogen atom, fluorine atom, Rf
CIf=CIf- or RfR3C, , CI! -] A fluorine-containing carboxylic acid or ester represented by the following.

■ A cyclic keto υ represented by the general formula 1 0 (wherein m represents an integer of 4 to 11) is reacted with hydrogen peroxide,
Then, the cyclic ketone bar that is produced is often represented by the general formula % [In the formula, Rf represents a fluoroalkyl group having 1 to 11 carbon atoms] or the general formula % [In the formula, Rf' is a fluorocarbon group] methyl group, R3 represents a methyl group] is reacted in the presence of a ferrous salt to form a compound of the general formula % [wherein A is CR/HCIf, f, or (CR
f/R3CH2)n (Rf is fluorocarbon having 1-11 carbon atoms
R is the same or different hydrogen atom, fluorine atom, R400CtCH2h (
R1, is a hydrogen atom or a lower alkyl group, m is 4-1'l
(@), RfCH-CH- or Rf/R3C=C
11-(Rf, Rf/ and R3 are the same as above), provided that R1 and R2 are both a hydrogen atom, a fluorine atom, R
1. A method for producing a fluorine-containing h-ruboxic acid or an ester thereof, which is characterized in that a compound represented by fCIl, Cl1- or RfR3 (but not CH-) is obtained.

Claims (1)

[Claims] ■ General formula % formula % [wherein A is CRfHCI (2+, or moCRiR
acHs++. , (R4 is a fluoroalkyl group having 1 to 11 carbon atoms, Rf is a fluoromethyl group, R8 is a methyl group,
n is an integer of 1 to 8), R1 and R2 are the same or different hydrogen atoms, fluorine atoms, R400C+ CfI! +
m (R4 is a hydrogen atom or a lower 7 /L/kyl group, m is 4
~11 integer), R4CH=CII- or R(RB C
=CH-(R(, R (and R8 is the same as above),
However, both R1 and R2 are hydrogen atoms, fluorine atoms, R(C
A fluorine-containing carboxylic acid or ester represented by H=CH- or Rf Rs C=CH-. ■ A cyclic ketone represented by the general formula [in the formula, m represents an integer of 4 to 11] and hydrogen peroxide are reacted,
Then, the generated cyclic ketone peroxides have the general formula % formula % [wherein Rf represents a fluoroalkyl group having 1 to 11 carbon atoms] or the general formula % formula % [wherein R'f represents a fluoromethyl group, R3 represents a methyl group] A monomer represented by the following is reacted in the presence of a ferrous salt to obtain the general formula % formula % [wherein A is +CR(HCH2+n or +CR(R
s CH2+n (Rf is a fluoroalkyl group of carbon ex-11, R'f is a fluoromethyl group, R8 is a methyl group, n is an integer of 1 to 8), R1 and R2 are the same or different hydrogen atoms, fluorine atoms ,R400CSoCTl2÷□
II (R4 is a hydrogen atom or lower 7 /L/ki/l/1
1, m is an integer from 4 to l), RfCH=CH- or R(
R8C=C11-(R(, R' (and RB are the same as above), provided that both R1 and R2 are hydrogen atoms, fluorine atoms, R(CH=CH- or RIRBC=C11-)) To obtain the compound represented by 11 yen
A method for producing a fluorine-containing carboxylic acid or an ester thereof.