JPS63146840A - Polyfluoro compound and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to perfluorinated chains (R
p) and a hydrogenated chain (R)I) at the same time.

Prior Art Fluorinated surfactants have the property of greatly reducing the surface tension of aqueous solutions and are therefore extremely useful in the preparation of extinguishing agents, especially mixtures of hydrocarbon extinguishing agents, for extinguishing fires. is important. In this fire extinguisher composition, fluorinated surfactants are generally combined with non-fluorinated surfactants to quickly form a fire-resistant and durable film on the surface of the water-insoluble hydrocarbon. Used in combination.

Problem that the invention seeks to solve: Although beneficial results are obtained by using mixtures of fluorinated and non-fluorinated surfactants, it is desirable to simplify the formulation of digestive compositions. For example, there is a need for a single surfactant that simultaneously contains perfluorinated and hydrogenated chains.

From this point of view, it is an object of the present invention to provide compounds comprising perfluorinated and hydrogenated chains.

Means for Solving the Problems The compounds according to the invention are represented by the following general formula: (in the above formula R1 represents a linear or branched perfluoroalkyl group containing from 1 to 20 carbon atoms;
RH represents a linear or branched alkyl group containing 1 to 18 carbon atoms, m represents a number from 0 to 2, χ represents OH
(R1 and R2 may be the same or different, and each is a hydrogen atom or a methyl group).

Particularly preferred is that the R1 and RH groups contain 4 to 12 carbon atoms and that the nitrogen is unsubstituted (R1=R2=
H) is a compound.

The invention furthermore relates to mixtures of two compounds of this type, one of which is represented by the formula: The other compound is represented by the formula: In the formula, m' is 1 or 2, and n is 1 to 17
is an integer, and the molar ratio of I-a/I-b is 0.
ranges from 1 to 10).

Compounds according to the invention in which X is an NR, R2 group include excess formamide or methane of formamide.

In the presence of the converted derivative, the following general formula: % formula % () (in the above formula, P is 0 or l, n is 1
(an integer from 17 to 17) can be synthesized by photoamidation of a polyfluorinated olefin.

This reaction is preferably carried out by irradiating a mixture containing the polyfluorinated olefin (II) and formamide or a methylated derivative thereof with ultraviolet light in the presence of acetone as an initiator.

This operation consists of 2-methyl-1-propanol, 1.4-
It is preferably carried out in a homogeneous medium consisting of a solution of the reactants (olefin, formacide and acetone) in an inert organic solvent such as dioxane, preferably tert-butanol.

Except in the case of dimethylformamide, microemulsions of the reactants obtained using nonionic surfactants and other surfactants of the alcohol type may be irradiated with ultraviolet radiation. One of the two surfactants mentioned above contains fluorine and the other is fluorine-free. Nonionic surfactants that can be used include, in particular, ethoxylated alkylphenols, polycondensates of ethylene oxide and propylene (Pluron 1
cs) ) and ethoxylated polyfluoroalcohols. Examples of other surfactants mentioned above include BhM group alcohols such as hexanol, heptatool and octatool; fluorofatties of the Rp C2H4OH type such as 2-perfluorobutylethanol and its perfluorohexyl and perfluoroctyl congeners; Examples include alcohols from the group alcohols. In order to obtain suitable microemulsions, nonionic surfactants and other surfactants as mentioned above are used in amounts such that the weight ratio ranges from 0.5 to 1.5, preferably approximately equal to 1. It is necessary.

From this point of view, combinations of a polycondensate of nonylphenol and 5 to 14 moles of ethylene oxide and 2-butyl perfluoroethanol, and a combination of a polycondensate of 2-hexyperfluoroethanol and 10 to 15 moles of ethylene oxide and 1- Combinations with hexanol, 1-heptatool or 1-octanol are particularly suitable.

Preferably, the irradiation is carried out at a temperature of 25 to 50°C;
The irradiation time can vary within a wide range depending on the intensity of the irradiation and is usually between 12 and 60 hours. The best yield is obtained when the irradiation time is 30 to 50 hours.

As before, the operation is carried out in the presence of excess formamide or its methylated derivative. The formamide (or methylated derivative)/olefin (II) molar ratio can vary over a wide range, but is generally IO to 12 to suit the photoamidation reaction and improve yields.
01 more preferably in the range of 40 to 90.

The amount of acetone used as initiator can vary within wide limits, but the acetone/formamide molar ratio is from 0.03 to 0.2, preferably from 0.05 to 0.09.
It is preferable to determine this amount so that it falls within the range of .

Selected method (homogeneous media or microemulsion)
Regardless, photoamidation of olefins of formula H produces a mixture of two amides:

(However, the symbols m', n, and Rp s R+ N R2 have the same meanings as above).

However, when the operation is carried out in a homogeneous medium, the corresponding 11-a amides are usually obtained, with the carbamoyl group fixed to the olefinic carbon furthest from the perfluoro chain. In the case of microemulsions, the major product is often the amide of the corresponding [[-b] in which the olefinic carbon closest to the perfluorocarbon is amidated. When it is necessary to separate amides ff1-a and m-b,
Separation can be achieved by conventional methods such as extraction with fluorinated solvents (eg trichlorotrifluoroethane) or pre-chromatography.

The starting material polyfluoroolefin (II) is a known substance. When P is 0 in the above formula, that is, the olefin RF-CH=CH-C,H21,,1 is usually
Perfluoroalkyl iodide R,I is added to olefin C7H2°, CH=CH2 (C.

Gui. Day, Tiers (G, V, D, TIER8
), “Journal of Organ
icmistry)” 27.2261.1962 and N.O., Brace (N.

0, BRACE), rorganic chemistry trace (JournaL
oforganicchemistry) J 37
．． 2429.1972), then the iodohydrin RFCH2CHI-C,,R2° produced. It can be obtained by dehydriodination of 1 with potassium hydroxide purified from alcohol. Further, when P is 1, that is, when the olefin RFCH2CH=CHC, R21,,1, the polyfluoroolefin is obtained by reacting -2-ethylperfluoroalkyltriphosphonium iodide with an aliphatic aldehyde. This 2-ethylperfluoroalkyltriphosphonium iodide is obtained by reacting 2-ethylpeterfluoroalkyl iodide with triphenylphosphine (Biniscura (B, ESCOUL)).
A) Others, “Synthetic Chemistry (Synthetic C.
15(1), 35, 1985
C, CECUTTI and others ``Journal of Dis
persion 5science and technology
ology) J,? (3), 307. 1986).

Compounds of the invention in which X is an OH group can be prepared by hydrolysis of amides. This hydrolysis can be carried out in an aqueous medium using a base. This base is preferably sodium hydroxide, but may also be potassium hydroxide. This operation is carried out for 12 to 36 N, preferably 2
100 to 160°C in a strong basic medium of 0 to 3ON
, preferably at a temperature of 120 to 140°C. Hydrolysis is believed to be complete after 24 hours. After acidifying the reaction mixture, the acid produced can be separated by conventional methods, in particular extraction using a solvent chosen among chlorofluorinated hydrocarbons, such as, for example, trichloro-trifluoro-ethane.

The acids according to the invention are oily or solid.

This acid can be easily converted to a water soluble salt by conventional methods. For example, it can be converted into a potassium salt by the action of an ethanolic potassium solution.

The polyfluorinated acids and their salts according to the invention are
It can be used as a surfactant or as an amide as an intermediate in the synthesis of surfactants and the like.

The following examples illustrate the invention but do not limit it in any way. The designation NMR"F spectrum indicates trifluoroacetic acid.

Example I L 1.1.2.2.3.3.4. Preparation of 4-nonafluoropentadecane-6 and 7-carboxylamide Fluorinated olefin Cs F s CH2CH= CHCa H+ 1.
0.744 g.

5.88 ml formamide, 15. tert-butanol.
84 ml and 0.83 mj2 of acetone are introduced. Next, a stream of argon is applied for 5 minutes to remove oxygen from the air.

Subsequently, attach the above tube to a rotating apple in a tubular jacket surrounded by 16 UV lamps (P = 300 nm, P = 16 W) kept at a temperature of approximately 30-35 °C, and expose it to UV light for 2 days. Expose to light.

Next, the bull diamide precipitate formed during the synthesis was removed by filtration, the filtrate was evaporated under vacuum (2000 Pa), and 5 mj of water! Collect the residue. It is purified by recrystallization in a mixture of equal volumes of acetone and petroleum ether and dried with P2O3 in an oven (666 Pa).

0.57 g of a solid melting at 80° C. is thus obtained. This solid was analyzed (NMR'H.

It is found to be an isomer of the following formula by NMRlgF and PVC): However, the a/b ratio is 2.89.

Example 2 1, l, 1.2.2.3.3.4.4.5.5.6.6
-) Production of Ridecaflu” orotrizocan-8 and 9-carboxylamide Fluorinated olefin Cs F + s CHz C
Work is carried out in the same manner as in Example 1, except that 0,832 g of H=CH-C,H is used. Solid melting at 78°C 0.58
g is obtained. When this is subjected to NMR and PVc analysis, it is found that it is an isomer pair of the following formula: Example 3 1, L 1.2.2.3.3.4.4.5.5.6.6
．． 7.7.8.8-Hebutadecafluoro-pentadecane-10 and 11-carboxylamide production Fluorinated olefin Ca F r t CH2CH=
Working in the same manner as in Example 1 using 91,032 g of CHC4H as a starting material yielded 0.98 g of a solid that melts at 88°C.
get. It is found by NMR and PVC analysis to be an isomer of the following formula: Example 4 1.1.1.2.2.3.3.4.4.5.5.6.6
．． 7.7.8.8-Hebutadecafluoro-eicosane-
9 and lO-Production of carfokimylamide Fluorinated olefin Cs F r q CH=CH-
C. If the procedure is carried out in the same manner as in Example 1 using 1.2 g of H2+ as a starting material, 0.82 g of a solid with a melting point of 92 DEG C. is obtained. It is an isomer of the following formula: Example 5 1.1.1.2.2.3.3.4.4-nonafluoro-
Preparation of pentadecane-6 and 7-carfokimyl acidIntroduce a microemulsion prepared from the following materials into a Pyrex tube.Fluorinated olefin C,F, -CH2-CH=CH
Co H++ 0.26 g = Formamide 1.48 g-2-
Perfluorobutylethanol 1.63 g-Polyethoxylnonylphenol (10.5 moles of ethylene oxide per mole of nonylphenol)
1.63 g-acetone
0.18 ml After degassing with argon as in Example 1 and irradiating for 2 days, the microemulsion is injected into the CPV and the following isomers are found to be present.

Example 6 ■,'', 1.2.2.3.3.4.4.5.5.6.6
．． 7.7.8.8-Hebutadecafluoro-eicosane-
Preparation of 9 and 10-carboxyl amides: Cs F lt CHCr , H23I
) To prepare CON H2, the fluorinated olefin Ca F lv
CH=CHCt. The work is carried out analogously to Example 5 using 1.63 g of four polyethoxylated nonylphenols with different numbers of ethylene oxides (EON) and 26 g of H210.

The results obtained are shown in the table below: Same fluorinated olefin Cs F l ? CH=C
In another series of experiments using HCr o H21, the same amount of polyethoxylated nonylphenol (
1,63 g) of fluorinated nonionic surfactant C11F13C2H4 (OC2H4)12 0H,j
: and the above 2-perfluorobutylethanol was replaced with the same amount (1.63 g) of each hydrogenated alcohol (1-hexanol, 1-heptatool, and 1-octanol). The results obtained are as shown in the table below: Example 7 1.1.1.2.2.3.3.4.4.5.5.6.6
．． 7.7.8.8-Hebutadecafluoro-eicosane-
Preparation of N-methyl-9-carboxylamide fluorinated olefin Ca F l ? CH=CHC
211.2 g of 10H and 8.65 g of N-methylformamide
If the same procedure as in Example 1 is carried out using mJ as the starting material, 1.1 g of a paste is obtained which melts at a temperature below 50°C. It is an isomer of: a/b
The ratio is 1.08.

Example 8 1.1.1.2.2.3.3.4.4.5.5.6.6
．． 7.7.8.8-Heptadecafluoroeicosane-N
- Preparation of methyl-9 and 10 carboxylamide A microemulsion prepared from the following starting materials is introduced into a pipe lettuce tube. Fluorinated olefin Ce F I? CH=C
H-C,. H210,26g -N-methylformamide 1.48g-
2-Perfluorobutylethanol 1.63 g-Polyethoxylated nonylphenol (12 moles of ethylene oxyoxide per 1 mole of nonylphenol)
1.63 g-acetone 0.18
m1 After degassing with argon and irradiating for 2 days as in Example 1, the microemulsion was injected and it was found that the following isomers were present.

Example 9 L L 1.2.2.3.3.4.4.5.5.6.6
．． 7.7.8.8-Hebutadecafluoroeicosane-N
, N-dimethyl=9 and 10-carboxylamide production Fluorinated olefin Ce F l ? CH=CH-
C. When working in the same manner as in Example 1 using 11.2 g of H2 and N,N-dimethylformamide as starting materials, 1.
11 g of oil are obtained. It is an isomer of the formula: CaF+t CHCl. H21 1(a) CON(CH3)2 C,F,, -CH-C,,H,3 1(b) CON(CH3)2 However, the ratio of a/b is 1.01.

Olefin CaF+t used in Examples 4 and 6 to 9
CH=CHCl0H21 was produced by the following procedure. 546 g of perfluorooctyl iodide and 5 g of azobisisobutyronitrile were prepared with a stirrer, a reflux condenser, and an outflow flask II! into the reactor. This mixture was heated to 75°C, then 261 g of 1-dodecene was added to 1
Implement it over time.

After 6 hours of reaction, azobisisobutyroni) IJ 2.
Add 5g and heat to 75°C for 4 hours.

Subsequently, the reaction mixture is distilled to remove excess perfluorooctyl iodide and dodecene (1 under 2666 Pa).
10 to 160°C). A solution of 68 g of potassium hydroxide in 250 ml of ethanol is then added to 678 g of the reaction product, keeping the temperature at 40-45°C. After adding water if and decanting, the organic phase (563 g) is separated and the olefin obtained is purified by distillation in vacuo (120° C./133 Pa).

Example 10 Preparation of L 1, ■, 2.2.3.3.4.4-nonafluoropentadecane-6 and 7-carboxylic acid In a flask equipped with a reflux condenser, 125 mg of the solid obtained in Example 1 A pasty mixture of , 2 mf water and 2 g sodium hydroxide is heated to 130° C. for 24 hours. After cooling the reaction mixture, 4.2 m of 37% hydrochloric acid was added.
1 to bring the pH to 1 and leave stirring for 3 hours.

Extraction of the aqueous phase with 1.1.2-trichloro-1,2,2-trifluoroethane and evaporation of the solvent gives 52 mg of a yellow oil. Analysis reveals that this is an acid with the following formula: Nishiki J (Jtl Infrared absorption spectrum: 2960 (free OH group); 1711 (C=O) 14
60 (CHαC02H):1236 (C-F)NM
R'H spectrum (CD3 COCD3): 0, 77
(3p Sm, CHa) 1, 16 (14p, mSCH2) 2.14 (1
pSmSCH) 3, 25 (4pSm, CH2a and βCF2) NM
RIgF spectrum (CD3 COCD3): 5.5
9 (3f, m, CFa) - 38,83 (2f,
m5CF2αCH2) 48.61 (2fSmSCF
2βCH2) 50.36 (2f, rnSCF2
αCF3) Example 11 ■, 1.1.2.2.3.3.4.4.5.5.6.6
-) Production of Ridecafluorotridecane-8 and 9-carboxylic acid Using 138 mg of the solid obtained in Example 2, Example 1
0, 100 mg of a yellow oil is recovered consisting of the following acid: Infrared absorption spectrum: 2969 (free OH groups): 1714 (C=O) 14
50 (HaCo2H): 120 g (C-F) Example 12 L 1.1.2.2.3.3.4.4.5.5.6.
6.7.7.8. Production of 8-heptadecafluoro-eicosane-9 and lO-carboxylic acid When the same operation as in Example 10 was carried out using 189 mg of the solid of Example 4, the following acid was formed. 63m of yellow oil
g is obtained: Infrared absorption spectrum: 2960 (OH radicals); 1720 (C=O)14
70 (CHαC02H); 1200 (C-F) NMR
'H spectrum (CD3 COCD3): 0, 92
(3p, mSCH3) 1.30 (18p, m5CH2) 2 (l p, m,, CH)

Claims (15)

[Claims] (1) The following general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, in the above formula, R_F is a linear or branched polyfluoroalkyl group containing 1 to 20 carbon atoms, R_H is a linear or branched alkyl group containing from 1 to 18 carbon atoms, m is an integer from 0 to 2, and X is an OH group or a NR_1R_2 group, in which case R_1 and R_2 may be the same or different. a hydrogen atom or a methyl group). (2) The polyfluoro compound according to claim 1, wherein R_1 and R_2 are hydrogen atoms. (3) A compound according to claim 1 or 2, characterized in that the R_F group and the R_H group each contain from 4 to 12 carbon atoms. (4) One compound has the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I - a), and the other compound has the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I-b), (wherein R_F is a linear or branched polyfluoroalkyl group containing from 1 to 20 carbon atoms and R_H contains from 1 to 18 carbon atoms. It is a linear or branched alkyl group, and X is an OH group or NR
_1R_2 groups, in the latter case R_1 and R_2 may be the same or different, but each is a hydrogen atom or a methyl group, m' is 1 or 2, n is an integer from 1 to 17), and I -a/I -b ratio from 0.1 to 10
A mixture of two compounds characterized in that (5) The following general formula: R_F-(CH_2)_p-CH=CH-C_nH_2
_n_+_1(II) (However, in the above formula, R_F is a linear or branched polyfluoroalkyl group containing 1 to 20 carbon atoms, P is 0 or 1, and n
is an integer from 1 to 17) in the presence of an excess of formamide or its methyl derivative, and if necessary hydrolyzing the resulting amide. General formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the above formula, R_F is a linear or branched polyfluoroalkyl group containing 1 to 20 carbon atoms, and R_H is a linear or branched polyfluoroalkyl group containing 1 to 20 carbon atoms. a linear or branched alkyl group containing 18 carbon atoms, p is 0 or 1;
X is an OH group or an NR_1R_2 group, and in the latter case, R_1 and R_2 may be the same or different, and each is a hydrogen atom or a methyl group. (6) The method according to claim 5, characterized in that the mixture of the olefin (II) and formamide or its methyl derivative is irradiated with ultraviolet light in the presence of acetone as an initiator. (7) The process according to claim 6, characterized in that the process is carried out in a homogeneous medium consisting of a solution of the olefin (II), formamide and acetone dissolved in an inert organic solvent. (8) The method according to claim 7, wherein the solvent is tert-butanol. (9) A microemulsion of the above olefin (II), formamide, and acetone was irradiated with ultraviolet rays using a nonionic surfactant, one containing fluorine, and one without fluorine, and another surfactant of the alcohol type. 7. The method according to claim 6, characterized in that the method comprises irradiating with. (10) The nonionic surfactant is selected from ethoxylated alkylphenols, polycondensates of ethylene oxide and propylene, and ethoxylated polyfluoroalcohols. The method described in Section 9. (11) The method according to claim 9 or 10, wherein the other surfactant is an aliphatic or fluoroaliphatic alcohol. (12) A patent claim characterized in that the nonionic surfactant is a polycondensate of 5 to 14 moles of ethylene oxide and nonylphenol, and the other surfactant is 2-butylperfluoroethanol. Range 9th
The method described in section. (13) The above nonionic surfactant is a polycondensate of 10 to 15 moles of ethylene oxide and 2-perfluorohexylethanol, and the other surfactant is 1
-hexanol, 1-heptanol or 1-octanol. (14) The molar ratio of formamide/olefin (II) is 1
0 to 120, preferably 40 to 90.
The method described in section. (15) Any one of claims 6 to 14, characterized in that the acetone/formamide molar ratio is from 0.03 to 0.2, preferably from 0.05 to 0.09. The method described in.