JPS60109548A - Fluorine-containing compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I {Rf is 3-21C fluorinated hydrocarbon or fluorinated polyoxyhydrocarbon; X<1> is group shown by the formula II [k is 0-6] which may be branched; X<2>-X<4> are 2-6C hydrocarbon; Y is group shown by the formula III [R<4> is H, or 2-4C acyl], group shown by the formula IV, etc.; m is 1-50; R<1> is H, or 1-5C hydrocarbon; R<2> and R<3> group shown by the formula V [q is 0-20 integer but not 0 at the same time], or -R<5>-Z [R<5> is 1-20C hydrocarbon, etc.; Z is -COOM (M is cation), etc.]}. EXAMPLE:A compound shown by the formula VI. USE:Useful as various kinds of wax, leveling agent for coating compound, water foamy fire-extinguishing agent, etc. Having good solubility in solvents, lowering extremely surface tension of solvent with a small amount of it. Having improved compatibility with a plasticizer for resin. PREPARATION:A compound shown by the formula VII is reacted with a compound shown by the formula RfCOA (A is alkoxy) to give a compound shown by the formula VIII (Y<1> is group shown by the formula VI, etc.), and this compound is reacted with a compound shown by the formula B-R (B is halogen; R is group shown by the formula V), to give a compound shown by the formula I .

Description

[Detailed description of the invention] The present invention relates to a novel fluorine-containing compound.

The novel fluorine-containing compound according to the present invention is as follows: , k is 0, n is 1
Indicates an integer between ~5. ], m is an integer of 1 to 50, and R1 represents hydrogen or a hydrocarbon having 1 to 5 carbon atoms. ] or -R5-
A group represented by z [However, R6 is a hydrocarbon group having 1 to 20 carbon atoms or (OR, OH.

00, 2Off, +”r (rFi, an integer from 1 to 5) 2 is 1000M (however, M represents a cation), M is the same as above) or R' -NHK ' (OX ” ) mOX ” N
YX' FL ((However, af, x'~x', Y, m
, R', R5 and M are the same as above. )]. )
It is a compound represented by

The Rf group in the novel fluorine-containing compound according to the present invention represented by the above general formula is a fluorinated hydrocarbon group having 8 to 21 carbon atoms or a fluorinated polyoxyhydrocarbon group, preferably having 5 to 15 carbon atoms. It is a fluorinated aliphatic group or a fluorinated polyoxyalkylene group.

Examples of this Rf group include straight chain A, branched "F(
2t+1) (however, t represents an integer from 3 to 21),
H(CjF--) (However, t is the same as above.) Indicates an integer. ) etc.

The hydrocarbon group contained in X2 to x4 and R1 to RIs in the general formula is preferably an alkylene group.

This alkylene group may be linear or branched if it has 2 or more carbon atoms.

M in the above general formula is a cation, usually hydrogen or an alkali metal cation, ammonium or N-substituted ammonium.

m in the general formula is an integer of 1 to 50, preferably 5 to 50.
It is an integer of 80. - represents an integer of J15 representing hydrogen or an acyl group having 2 to 4 carbon atoms. ], and the above RV is usually hydrogen. This Y usually originates from the method for producing the novel fluorine-containing compound according to the present invention shown below.

The novel fluorine-containing compound according to the present invention is usually a compound represented by the formula (a): %formula% (wherein R1, 12 to x4 and m are the same as above) and the formula: (wherein, fLf and xl is the same as above), (in the formula,
R is the same as above, and m represents an alkoxy group. ) Formula: %Formula%(3) (In the formula, Rf is the same as above, B represents a halogen.), Formula: %Formula%(4) (In the formula, Rf, xl and B are the same as above.) Or the compound i represented by the formula: %formula% (5) (in the formula, R (, X' and B are the same as above) is reacted at a molar ratio of 1.l, , af, x', x', A, B, m and n
or (Of(, +. [However, n is the same as above.]) ゛ is obtained, (b) the compound obtained in the above (a) and the formula: %formula%( 6) [However, 几5 and zFi are the same as above.] It can be obtained by reacting with a compound represented by the following formula at a molar ratio of t-1:1 or 1:2.

(a) and (b) are shown below in reaction formula.

■Ninka Mitsuji, 2'R*+=I%() - 1 Rujo Usually, the solvents used in reaction (1), (2) or (5) are alcohols, ethers, hydrocarbon compounds, For halogenated hydrocarbon compounds, aromatic compounds, etc., the reaction temperature is 20 to 15 liters, preferably 40 to 100 liters, and the reaction time is 8 to 10 hours, preferably 5 to 8 hours.

'Usually, the solvent used in reaction (3) or (4) is an ether, a hydrocarbon compound, a halogenated hydrocarbon compound, an aromatic compound, etc., and the reaction temperature is -10 to 100°C.
Preferably the temperature is 0 to 50°C, and the reaction time is 1 to 5 hours, preferably 2 to 8 hours.

Usually, reaction (6) is carried out after completion of reaction 1.2.3.4 or 5 without isolating the product by adding the formula: B-IL (where R and L are the same as above) to the reaction mixture. ) is added in an equivalent amount or twice the equivalent amount, and the reaction temperature is 20 to 150°C, preferably 40 to 100°C.
After the reaction (6) is completed, an acid halide or an acid anhydride may be added to the reaction mixture and the reaction may be carried out at around room temperature.

Next, specific examples of the novel fluorine-containing compound according to the invention will be shown, but of course the present invention is not limited to these.

(L large "F - all white, Yu momme ship L; small shin ″!El:E Conventional method: (In the formula, fLf is the same as above.) (In the formula, Rf is the same as above.) (In the formula, Rf is the same as above.) Fluorine-containing compounds represented by the following are known.

This conventional fluorine-containing compound is used as a leveling agent for various waxes and paints, as an additive for fire extinguishing foam, and as a bottom surface modifier for resins, but it has poor solvent solubility, and even when dissolved in a solvent, it remains It has a poor ability to lower the surface tension of solvents,
Further, there are drawbacks such as poor compatibility of the resin with the plasticizer.

The new fluorine-containing compound according to the present invention has the same structure as the above-mentioned conventional fluorine-containing compounds, which are diamines. ) or -ni'-Z (However, 1L5 and 2 are the same as above.)
They differ in that they are bonded with a group that can be expressed as As a result, the new fluorine-containing compound according to the present invention has better solvent solubility than the conventional fluorine-containing compounds described above, has the effect of greatly increasing the surface tension of the solvent even in a small amount, and is also effective as a plasticizer for resins. Because of its excellent compatibility with various waxes and paints, it can be used as a leveling agent for various waxes and paints, as an additive for aqueous fire extinguishing foams, synthetic surfactants or protein foam fire extinguishers, powder fire extinguishing agents, fibers,
It can be suitably used as a penetrating agent for processing liquids for metals, photographs, etc., an antistatic agent for resins, an anti-adhesive agent, an antifouling agent, an anti-fogging agent for agriculture and films, a mold release agent, an emulsifier for emulsion polymerization, etc.

Next, synthesis examples, test examples, and comparative examples of novel fluorine-containing compounds according to the present invention will be shown.

Synthesis Example 1゜■ (Ck128Acu2α)ONa I') Synthesis) (&
) C3F1. Cf120ft (J25.
25g (0.01 mol), H2N(cii2) 8o(
(a■, ) 4o) 8(cu, ).

27.08 g (0.01 mol) of NH and 15 gk of Improper Tool were charged and reacted at 70° C. for 6 hours. When the reaction mixture was analyzed by gas chromatography, no raw material epoxide compound was detected.

(b) Add ClCH2000f to the reaction mixture obtained above.
0.95 g (0.01 mol) of lI and NaONaOH
0J30.02 mol) was further added thereto, and the mixture was reacted at 70°C for 7 hours. Improper tool was then eluted from the reaction mixture, and the residue was washed with a mixture of acetonitrile and trichlorotrifluoroethane in a weight ratio of 50:50. 12.22 g (yield: 98 g) of solid was obtained.

The compound obtained above was analyzed by nuclear magnetic resonance (NMR) and infrared absorption (IR) and was identified as the title compound. The analysis results are shown below.

"F-NMR (OF, 0OOHt - used as external standard.)
(Koyu Kochi, Electricity Collection 1: War Hi〈) '11-NMR' There was one absorption of the carbonyl group of 10H1ICOONa at 21 1610+++'.

Synthesis Example 2 The same reaction as in C&) of Synthesis Example 1 was carried out, and 61 g (0.02 mol) of CICH, OH, OJ and 0.80 g (0.02 mol) of NaOH were added to the resulting reaction mixture,
The reaction was carried out at 70°C for 7 hours. After the reaction was completed, the inpropatol was eluted from the reaction mixture, and the residue was mixed in a weight ratio of 50:50.
The residue was washed with a mixture of acetonitrile and trichlorotrifluoroethane to obtain 12.08 g (yield: 91 tIb) of the title compound. The NMR analysis results are shown below.

19F -NMR α-T-containing, [missively rounded] n-NMR Synthesis example 3゜0 (C7'16 deception (CJlt2), O ((cii2)4o
), (an,)8(&)c7r16co in a 100ml 1-4 flask equipped with a thermometer, condenser and stirrer.
,c,u,4. +2g (0.01 mol), H2N(OH
2), 0 ((OR,), 0') 8 (OH,), N town 7.
08g (0,01 mol) and Impropatool 15g
was charged and reacted at 70°C for 7 hours. When the reaction mixture was analyzed by gas chromatography, no starting ester compound was detected.

(b) Add ctCl to the reaction mixture obtained in (a) above.
.

Of(, OK 1.61 g (0,02&) and N
a ouo, a Og (0.02 mol) was added and reacted in the same manner as in Synthesis Example 2 to give 10.7 g (yield: 9
The title compound of 0ch) was obtained. The results of elemental analysis and IR analysis are shown below.

100m equipped with elemental analysis (&) thermometer, cooler and stirring device
1 four low frus = + c8ir1. an, an2s
o, a16.47 g (0.01 mol) u, N(a
n, ), O((C!Hri 40)27(CII2)
-Machi 2O, sg (o, ot mol) and 20g of trichlorotrifluoroethane were charged and reacted for 80 minutes while cooling to 0°C, and then further reacted for 2 hours at room temperature.

(b) n1 reaction mixture K C10NgOH2 obtained above
0HIB 1g (0.02 mol) and Na(M(0
, 80g' (0.02 mol) was added and reacted in the same manner as in Synthesis Example 2 to obtain 24.6g (yield: 92mm) of the title compound.

The results of elemental analysis and IR analysis are shown below.

There was absorption by -OR, 80□N〈at 1,170m in one construction. 7 Synthesis Example 5. H (a) 100 equipped with thermometer, cooler and stirring device
m1 (1) 08F, 70H, CH2 in a Yotsuro flask
l5.74 g (o, o t mol), [2N(OH2)
80 ((OH2).

0) 18 (CII2), ffi, 10.7g (0,
01 mol) and 15 g of Improper Tools,
The reaction was carried out at 70°C for 6 hours. When the reaction mixture was analyzed by gas chromatography, the above iodide was not detected.

0) Add Cl0H20ff280 to the reaction mixture obtained above.
゜Na 1.67g (0.01 mol) and NaOH
0.40 g (0.01 mol) was added and reacted in the same manner as in Synthesis Example 2 to obtain t4.6 g (yield 89%) of the title compound. The results of elemental analysis are shown below.

The same reaction as in Synthesis Example 1 (a) was carried out, and 1.9 g (0.02 mol) of CLCHzCooH and 1.6 g (0.04 mol) of NaOH were further added to the resulting reaction mixture, and the same reaction as in Synthesis Example 1 was carried out. The reaction yielded 12.5 g (yield: 90 g) of the title compound. The results of elemental analysis are shown below.

Test Examples and Comparative Examples (I) Solubility in organic solvents of the novel fluorine-containing compounds according to the present invention and comparative examples below and 1) Toluene surface tension when dissolved at 0.1% by weight in toluene, that is, surface tension Shows decreasing ability.

The surface tension of NaO and toluene was measured using the Wilhelmy method.

(P Shimojo himself, I'm afraid of the damage) ′″″ ′″′ Government 8 Q u Ri Hibiki Σ Award! Small 33 (I) Solubility in organic solvents In the table, ○ indicates soluble, △ indicates slightly opaque or Dispersed state, × indicates insoluble.

(ll) Surface tension of toluene when 0.1 weight 1 itIb is dissolved in toluene (surface tension of toluene 28.5 dyne 15+) Compound ←1) cannot be measured because it is insoluble in toluene. Above is a continuation of page 1 Procedural amendment (spontaneous) 9/9/1980 1, Indication of the case 1988 Patent Application No. 217583λ Name of the invention Fluorine-containing compound 3, Person making the amendment Related Patent applicant address New Hankyu ψ 39, Umeda 1-chome, Kita-ku, Osaka (285) Daikin Industries, Ltd. Explanation 6, details of correction.

■The following sections in the detailed description of the invention in the specification will be amended.

(1) Page 3, line 2, r(-CH+kJ)
+ CH2+* Correct to J.

(2) Page 3, line 10, “1-20” is 10-2
Correct 6 positions to 0.

(3) On page 3, line 11, add "1 and 0 cannot be equal to 0 at the same time" next to "indicate". '(4) 1st ay@1
row, “C6F17 CH2CH2N(CH2)sCH2
0CH2C) 12503 Join NaJ.

(CH3) Corrected to 2j.

(9) Chemical shift grip in the table on page 19 2, 58-2,
900 attribution, mafc is through or > NCH
2CH, -j > Corrected to be published by NCH2CHr.

90 Page 30, line 3 to line 32, two lines from the bottom, ``In the comparative example...impossible,'' has been revised as follows.

Nku:h:C1(,oH(v...).

(CH2)3NH2(xi,) FC-430 (fluorine thread surface active agent manufactured by 3M Company) (xi
i) (1) Yes+4 In the table, ○ indicates soluble, 6 indicates slightly opaque or dispersed state, and X indicates insoluble.

(Company) Surface tension of toluene when dissolved in 0.1 liters of toluene (surface tension of toluene 28.5 dynes/
1) Compound (x) cannot be determined because it is insoluble in toluene. (Attachment) Amended claims (1) General formula: (In the formula, R/ is a fluorinated hydrocarbon group or a fluorinated polyoxyhydrocarbon group having 3 to 21 carbon atoms, and Xi is branched. +(, R2-), (where k represents an integer of θ to 6), X2 to x4 are the same or different hydrocarbon groups having 2 to 6 carbon atoms;

? R" Y is -CH-CH2- (however, R4 is hydrogen or carbon or +C) 12+1. (however, 11 represents an integer of 1 to 5), mFit- an integer of trout, R1 is hydrogen or carbon number 1
-5 ashing hydrogen group, R1' and R3 are the same or different +x20, H [however, x2 is the same as above, 9 is 0
Indicates an integer between ~20, but never 0 at the same time. ] or a group represented by -R5-Z, provided that BS has 1 to 1 carbon atoms
20 hydrocarbon groups or -f-CH,CI(,OCH,
CH2-)-r (where r represents an integer of 1 to 5)Z
is -COOM (where M represents a cation), -8
03M (However, M is the same as above.), -0803M
(However, Mta is the same as above.), -o) (oM)2
(However, Mrt is the same as above.) Or (However, R1%X' ~ X', Y, m%R'
, R' and M are the same as above. )]. ) A fluorine-containing compound represented by

that's all

Claims (1)

[Claims] (In the formula, Rf is a fluorinated hydrocarbon group or a fluorinated polyoxyhydrocarbon group having 8 to 21 carbon atoms, xl is a branched (CH,%) [where k is θ x2 represents an integer of 1 to 5; m represents an integer of 1 to 50;
R1 represents hydrogen or a carbonized integer having 1 to 5 carbon atoms. ],
or a group represented by -R6-Z [however, R6 has 1 carbon number]
~20 hydrocarbon groups or %CH, (3H!!OCR,
CH,+, (-r[1-517) indicates an integer. ) z bar cooMc However, M represents a cation. )
,, -808M (However, M is the same as above.) or (However, Rf, Xl-X4, Y, m%R', n'ox
Him is the same as above. )]. ) A fluorine-containing compound represented by