JPH10237130A - Fluorine-containing nitrile and its polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound obtainable in a relatively good yield and having good storage stability and high polymerization activity. SOLUTION: This compound is represented by the formula CH2 =CFCF2 O-(CF2 O)x -(CF2 CF2 O)y -(CX<1> 2 CF2 CF2 O)z -(CFX<2> CF2 O)w -CFX<3> -CN [X<1> is H, F or Cl; X<2> is H or Cl(trifluoro)methyl; X<3> is H, F, Cl or trifluoromethyl; (x), (y), (z) and (w) are each 0-20 and the sum of (x), (y), (z) and (w) does not exceed 20], e.g. a compound of the formula CH2 =CFCF2 O-CF(CF3 )-CN. The compound of the formula CH2 =CFCF2 O-(CF2 O)x -(CF2 CF2 O)y -(CX<1> 2 CF2 CF2 O)z )-(CFX<2> CF2 O)w -CFX<3> - CN is obtained by removing FI from terminal iodine nitrile of the formula ICH2 CF2 CF2 O-(CF2 O)x -(CF2 CF2 O)y -(CX<1> 2 CF2 CF2 O)z -(CFX<2> CF2 O)w -CFX<3> -CN in a solvent (e.g. dimethyl-formamide) in the presence of a catalyst (e.g. zinc) at a temp. of -20 to 200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine-containing nitrile and a polymer thereof, and more particularly, to a fluorine-containing organic compound having a vinyl group, an ether group and a cyan group and a polymer thereof.

[0002]

2. Description of the Related Art It is known to introduce a functional group into a polymer by polymerizing a monomer having a functional group (for example, a vinyl group or a cyan group) and use it as a reactive site such as a crosslinking site. For example, US Pat.
No. 6186, No. 3933767, No. 428109
In No. 2, etc., a perfluoroelastomer crosslinked product is obtained by copolymerizing a perfluorovinyl ether containing a cyan group to form a perfluoropolymer and trimerizing through a cyan group. In addition, U.S. Pat.
No. 031124 describes a method for synthesizing this kind of monomer.

[0003] However, the perfluoro compounds described in the above-mentioned prior patents are complicated in synthesis method, low in yield, and consequently expensive. In addition, perfluorovinyl ether has low stability to oxygen and does not have high polymerization reactivity.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel fluorine-containing nitrile which can be obtained at a relatively high yield, has a good storage stability, and has a high polymerization activity.

[0005]

SUMMARY OF THE object of the present invention have the general _{formula: CH 2 = CFCF 2 O- (} CF 2 O) x - (CF 2 CF 2 O) y - (CX 1 2 CF 2 CF 2 O) z -(CFX ² CF ₂ O) _w -CFX ³ -CN (I) (wherein, X ¹ is a hydrogen atom, a fluorine atom or a chlorine atom, X ² is a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group , X ³ represents a hydrogen atom, a fluorine atom, a chlorine atom or a trifluoromethyl group, and x, y, z and w each independently represent a number from 0 to 20, provided that
The sum of x, y, z and w does not exceed 20. ) -Containing fluorine-containing nitrile having a molecular weight of 1,000 to 1,000,000
Fluorinated nitrile polymer having a molecular weight of 1,000 to 1,000,000 and a content of the fluorinated nitrile of 0.1 to 99 mol% and other copolymers Provide copolymers with possible monomers. Preferred examples of the fluorine-containing nitrile (I) _{is, CH 2 = CFCF 2 O-} CF (CF 3) -CN, CH 2 = CFCF 2 O-CF (CF 3) CF 2 0-CF (C
F ₃₎ -CN, and _{CH 2 = CFCF 2 O- [CF} (CF 3) CF 2 0] 2 -CF (C
F ₃ ) -CN. In order to simplify each general formula, in the following description,-(CF ₂ O) _x- (CF ₂ CF ₂ O) _y- (CX ¹ ₂ CF ₂ CF ₂ O) _z- (CFX ² CF
₂ O) _w -CFX ^3- is represented by Rf.

The fluorinated nitrile (I) of the present invention is obtained by converting a terminal iodine nitrile represented by a general formula: ICH ₂ CF ₂ CF ₂ ORfCN (II) (where Rf is as defined above) Solvents (eg, dimethylformamide, dimethyl sulfoxide, methyl alcohol,
Acetone, methyl ethyl ketone, ethyl acetate, etc.)
It can be easily synthesized by removing FI in the presence of a catalyst (for example, zinc, copper, etc.). The reaction temperature is
The temperature is from -20C to 200C, preferably from 50C to 150C.

The starting iodine nitrile (II)
Is a general formula: ICH ₂ CF ₂ CF ₂ ORfA (III) wherein Rf is as defined above.
F, COOH or COOR (where R represents 1 to 1 carbon atoms)
10 organic groups. ). ) Can be derived by known methods (for example, see US Pat. No. 4,138,426).

As an example, ICH ₂ CF ₂ CF ₂ ORfCN
Is shown below.

Embedded image ICH ₂ CF ₂ CF ₂ ORfCOF + CH ₃ OH → ICH ₂ CF ₂ CF
₂ ORfCOOCH ₃ 2. ICH ₂ CF ₂ CF ₂ ORfCOOCH ₃ + NH ₃ → ICH ₂ CF ₂ CF ₂ ORfCONH
₂ 3. ICH ₂ CF ₂ CF ₂ ORfCONH ₂ → ICH ₂ CF ₂ CF ₂ ORfCN

The fluorinated nitrile (I) of the present invention, when trimerized, has the general formula:

Embedded image (Wherein, Rf is as defined above). This triazine compound (IV) has high activity and is useful as a crosslinking agent for polymers.

The trimerization of fluorinated nitriles (I) is described, for example, in J. Org Chem. 32, 231 (1967). First, two molecules of the nitrile are reacted in the presence of NH ₃ to give CH ₂ ＣＦCFCF ₂ OR
_{fC (NH 2) = N-} C (= NH) -RfOCF 2 CF = CH
_{Get two} . The reaction temperature is not particularly limited.
The temperature is 100 ° C., preferably −30 ° C. to 50 ° C., and the reaction pressure is not particularly limited, but can be applied from reduced pressure to increased pressure.
The higher the temperature, the faster the reaction. However, the temperature needs to be lowered to maintain the concentration at atmospheric pressure due to NH ₃ gas. If a pressure vessel is used, it is possible to react quickly at room temperature, for example. The reaction solvent is aprotic and can be used without any particular problem as long as it can be mixed with the nitrile. For example, tetrahydrofuran, dimethylformamide, acetone and the like. It is advisable to dehydrate before use so as not to contain water.

The obtained CH ₂ = CFCF ₂ ORfC (N
_{H 2) = N-C (} = NH) to -RfOCF ₂ CF = CH _{2, 2}
By reacting twice the molar amount of CH ₂倍 CFCF ₂ ORfCOZ (where Z is a halogen atom, for example, a fluorine, chlorine, bromine or iodine atom), the desired triazine compound is obtained. The reaction temperature is not particularly limited, but is -50 ° C to 100 ° C, preferably 0 ° C to 50 ° C. The reaction pressure is not particularly limited, but should be determined according to the boiling point of the compound used. I can do it. The reaction solvent is not particularly limited, but an aprotic solvent containing no water is used. For example, tetrahydrofuran, dimethylformamide, acetone and the like. When triethylamine or the like is added as an acid acceptor during the reaction, the reaction proceeds easily.

[0012] The reaction can also be reacted with excess NH ₃ amount to the nitrile initially, first CH ₂ = CFCF ₂ ORfC
After obtaining (NH ₂ ) = NH, equimolar CH ₂ ＣＦCF
By reacting CF ₂ ORfCN, C
H ₂ = CFCF ₂ ORfC (NH ₂ ) = NC (= NH) -R
fOCF ₂ CF = CH ₂ was obtained, and two times the mole of C
It can also be carried out by reacting H ₂ = CFCF ₂ ORfCOZ. CH ₂ = CFCF ₂ ORfC
The reaction conditions for obtaining (NH ₂ ) = NH are the same as in the above reaction except that NH ₃ is used in excess.

CH ₂ = CFCF ₂ ORfC (NH ₂ ) = NH
And reaction conditions of CH ₂ = CFCF ₂ ORfCN is not particularly limited, the reaction temperature is -50 ° C. to 100 ° C., preferably from 0 ° C. to 50 ° C.. There is no restriction on the pressure. The solvent is not particularly limited, but an aprotic solvent containing no water is used. For example, tetrahydrofuran,
Dimethylformamide, acetone and the like. CH ₂ =
CFCF ₂ ORfC (NH ₂ ) = NC (= NH) -RfOC
The reaction of F ₂ CF ＝ CH ₂ and CH ₂ ＣＦCFCF ₂ ORfCOB can be similarly carried out for different combinations of x, y, z and w in Rf. By this method, a triazine ring can be obtained with any combination of nitriles.

The fluorinated nitriles (I) of the present invention can be polymerized by homopolymerization of one kind or by copolymerization of two or more kinds thereof. It can also be copolymerized. Other copolymerizable monomers include tetrafluoroethylene, vinylidene fluoride,
Examples thereof include perfluoroalkyl vinyl ethers such as hexafluoropropene, perfluoromethyl vinyl ether and perfluoropropyl vinyl ether, hexafluoroisobutene, trifluoroethylene, vinyl fluoride, chlorotrifluoroethylene, ethylene, propylene, butadiene, and alkyl vinyl ether.

The polymerization of the fluorinated nitrile (I) of the present invention can be carried out by a general polymerization method under general polymerization conditions. Preferably, radical polymerization (bulk polymerization, solution polymerization, emulsion polymerization, etc.) using a radical initiation source is employed. The reaction conditions in the radical polymerization are not particularly limited, and include a temperature selected from a temperature of 0 to 100 ° C., an atmospheric pressure, a reduced pressure of about 76 cmHg, or a pressure of about 100 kg / cm ² G.

The fluorine-containing nitrile of the present invention can be used as a monomer for homopolymerization or copolymerization to introduce fluorine and cyano groups into the polymer. In addition, a functional group can be advantageously introduced into the polymer by utilizing a cyan group to crosslink a triazine or to a carboxylic acid. Triazine cross-linking of a cyan group can be used as a cross-linking of high-performance, heat-resistant fluororubber.On the other hand, by making the cyano group of a homopolymer or a copolymer a carboxylic acid,
The polymer can be used as a polymer electrolyte and used as an electrolyte for a battery. Also, ionic crosslinking is possible. A crosslinked polymer (rubber) having a cyano group as a side chain can also be obtained by utilizing the HF removal reaction of the main chain. Further, a polymer having a cyano group as a carboxylic acid can be used as an ion exchange resin, a superabsorbent polymer, or the like. Further, a trifunctional unsaturated compound obtained by trimerization using a cyan group can be used as a crosslinking agent or the like.

[0017]

EXAMPLES Example 1 25 g of ICH ₂ CF ₂ CF ₂ CF (CF ₃ ) CN, zinc powder 1
5 g and 10 ml of dimethylformamide (DMF)
Placed in a flask, which was heated on a 160 ° C. oil bath.
After a while (about 40 minutes), a sudden reaction occurred.
Thereafter, the mixture was refluxed at 71 ° C. and the reaction was continued for 1 hour. After the completion of the reaction, the reaction mixture was subjected to simple distillation under normal pressure to obtain 2.43 g (purity: 99.4%) of a product. Boiling point 71 ° C.
The structure of the product was determined by IR, GCMS and NMR (H, F)
And confirmed that CH ₂ = CFCF ₂ CF (CF ₃ ) CN
Met. FIG. 1 shows the IR chart.

Example 2 50 g of ICH ₂ CF ₂ [CF ₂ OCF (CF ₃ )] ₂ CN, 20 g of zinc powder and 10 ml of DMF were placed in a flask, which was heated on a 160 ° C. oil bath. After a while (about 6
After 0 min) a sudden reaction occurred. After completion of the reaction, the reaction mixture was distilled under normal pressure to obtain 7.77 g of a fraction (purity: 74%, unreacted substance: 11%, DMF: 13%). This was purified by simple distillation to obtain a product having a purity of 98.6%. Boiling point 1
08-112 ° C. The structure of the product was confirmed by IR, GCMS, and NMR (H, F) to find that CH ₂ ＣＨCF [C
F ₂ OCF (CF ₃ )] ₂ CN. Fig. 2 IR chart
Shown in

Example 3 CH ₂ = CF [CF ₂ OCF (CF ₃ )] ₂ CN (hereinafter referred to as “AC
N2) 5 g, [H (CF ₂ CF ₂ ) ₃ COO] ₂ /
0.5 g of C ₂ F ₃ Cl ₃ (8% by weight) was mixed in a glass container, the atmosphere in the container was replaced with nitrogen, and the mixture was stirred at room temperature. As a result, the viscosity of the mixture increased. The low-boiling substances were distilled off from the reaction mixture under reduced pressure to obtain 2.82 g of a colorless, transparent and viscous polymer. From the results of IR, ¹ H-NMR and ¹⁹ F-NMR, it was confirmed that the produced polymer was a polymer containing an unsaturated bond. The structure is

Embedded image Met. As calculated from the yield and NMR results, the number average molecular weight was about 35,000 to about 48,000.

Examples 4 to 6 In the same manner as in Example 3, ACN2 and CH ₂ = CF ₂ , CF
₂ = CF ₂ or CF ₂ = CF ₂ / CF ₃ CF ₂ CF ₂ O [CF
Copolymerization with (CF ₃ ) CF ₂ O] ₂ CF = CF ₂ (φVE) was performed. Table 1 shows the results.

[0021]

[Table 1]

EXAMPLE 7 1225 g of pure water, CF
₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COON
H ₄ 122.5 g, NaCl ₄ g, Na ₂ SO ₃ 2.155
g and CF ₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] ₂ CF
= CF ₂ , and the atmosphere in the autoclave was replaced with nitrogen and then with CF ₂ = CF ₂ ,
Then, the internal pressure was adjusted to 2.5 kg / cm ² G with CF ₂ = CF ₂ , and then a solution prepared by dissolving 24.5 mg of ammonium persulfate in 10 ml of pure water was charged. As the polymerization proceeds, the pressure becomes 2.5
Kg / cm ² G, then ICF ₂ CF ₂ CF ₂ CF ₂
211.57 g was charged. Further, the pressure is 1.5 kg / cm
^{When the} pressure reaches ² G, the pressure is increased to 2.5 kg / CF ₂ with CF ₂ = CF _2.
cm ² G.

Similarly, when the polymerization pressure dropped to 1.5 kg / cm ² G, CF ₂ = CF ₂ was charged again from the cylinder, and the pressure was returned to 2.5 kg / cm ² G. At this time, the weight of CF ₂ = CF ₂ is set to reduce the weight of the cylinder. This procedure was repeated, and when polymerization proceeded further, and a total of 50 g of CF ₂ = CF ₂ was charged, 2.79 g of ACN2 was charged. The polymerization rate became extremely slow when ACN2 was charged, but the polymerization rate recovered within a while. Further complete the _{polymerization,} was charged 2.79g of CF 2 = CF ACN2 again in ₂ the place were charged a total of 100g. As in the previous case, a decrease in the polymerization rate was observed, but it was recovered in the same manner.
The polymerization was stopped when a total of 140 g of CF ₂ = CF ₂ was added. Residual gas monomer was blown to 1892.2
A dispersion of g was obtained. The solids content was 20.87% by weight. The polymerization time was 154 minutes in total. Hydrochloric acid was added to the resulting dispersion to coagulate, washed with acetone, and heated to 120 ° C.
To obtain a white rubbery polymer. The composition of this polymer is CF ₂ = CF ₂ / φVE / ACN ₂ = 76.
It was 4 / 22.8 / 0.8 (molar ratio). The Mooney viscosity was ML _{1 + 10} (100 ° C.) = 41.5.

Example 8 The addition of ACN2 was repeated and the total charged amount of CF ₂ = CF ₂ was 2
A rubbery polymer was obtained in the same manner as in Example 7, except that the test was carried out also at 5 g and 75 g. When IR was measured by using the polymers obtained in Examples 7 and 8 as thin films, absorption near 2250 cm ^-1 based on -CN was observed in each case.
The composition of this polymer is CF ₂ = CF ₂ / φVE / ACN ₂
= 76.1 / 22.7 / 2.2 (molar ratio). The Mooney viscosity was ML _{1 + 10} (100 ° C.) = 40.

Example 9 100 parts by weight of the polymer obtained in Example 8 was kneaded with 3 parts by weight of tetraphenyltin using a 3-inch rubber roll,
Press vulcanization at 0 ° C. for 1 hour gave a colorless and transparent thin film vulcanized rubber. In the IR of this thin film, the absorption based on -CN disappeared, and the absorption at 1550 cm ^-1 based on the triazine ring was observed.

Example 10 CH ₂ ＣＦCFCF ₂ OCF (CF ₃ ) CN
At 15 ° C., 15 g of NH ₃ was charged, the temperature was gradually raised to room temperature, excess NH ₃ was released at atmospheric pressure, reacted overnight, and CH ₂ ＣＦCFCF ₂ OCF (CF ₃ ) C (N
H) = NH was obtained. (The structure was confirmed by IR and NMR.) The obtained CH ₂ ＣＦCFCF ₂ OCF (CF ₃ ) C (NH) ＝ N
H 25.4 g in equimolar CH ₂ ＣＦCFCF ₂ OCF (CF ₃ )
23.7 g of CN was reacted, and CH ₂ ＣＦCFCF ₂ OCF (C
_{F 3) C (= NH)} -N-C (NH 2) CF (CF 3) OCF 2 C
F = CH ₂ was obtained. (The structure was confirmed by IR and NMR.) This CH ₂ ＣＦCFCF ₂ OCF (CF ₃ ) C (＝ NH) —N—
_{C (NH 2) CF (CF} 3) OCF 2 CF = CH 2 4.91g twice moles of _{CH 2 = CFCF 2 OCF (CF} 3) COF5.1
When 6 g was added, a mild exotherm was observed. Then, a white solid precipitated, but after a while, it became colorless and transparent. At this point, the formation of triazine was confirmed by IR of the reaction mixture, but it was also confirmed that unreacted raw materials remained. When 3.03 g of triethylamine was added thereto, the mixture reacted exothermically, and the solution was colored yellow-brown. From IR (FIG. 3), it was confirmed that the raw material was completely reacted to produce a triazine of the following formula. .

[0027]

Embedded image

Embodiment 11 In the same manner as in Embodiment 10, CH ₂ ＣＦCFCF ₂ OCF (C
F ₃ ) C (NH) = NH is reacted with an equimolar amount of ACN2,
_{H 2 = CFCF 2 OCF (CF} 3) C (= NH) -N-C (NH
_{2) [CF (CF 3)} OCF 2] to give the ₂ CF = CH _2. This is 2
The following compound was obtained by adding twice the molar amount of CH ₂ ＣＦCFCF ₂ OCF (CF ₃ ) COF and triethylamine.

[0029]

Embedded image Example 12 CH ₂ ＣＦCFCF ₂ OCF obtained in the same manner as in Example 10.
_{(CF 3) C (= NH} ) -N-C (NH 2) CF (CF 3) OCF 2
The following compound was obtained by adding twice the molar amount of CH ₂ ＣＦCFCOF and triethylamine to CF ＝ CH ₂ .

[0030]

Embedded image

Example 13 Triazine [CH ₂ ＣＦCFCF ₂ OCF obtained in Example 10
To 0.1 g of (CF ₃ ) CN] ₃ , 0.1 g of an organic peroxide (Perhexa-2,5-B; manufactured by NOF CORPORATION) was added, and heated to 160 ° C. in an oil bath. A hard resinous material was obtained.

Example 14 In the same manner as in Example 13, 0.5 g of the triazine obtained in Example 10 and 0.1% of triallyl isocyanate (TAIC) were added.
And 5 g of perhexa-2,5-B0.1.
g, and heated to 160 ° C. on an oil bath, and reacted rapidly to obtain a hard resinous material.

Example 15 and Comparative Example 1 Tetrafluoroethylene having iodine at both ends and CF
₃ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] ₂ CF = CF ₂ copolymer rubber (tetrafluoroethylene content: 77 mol%. Mooney viscosity ML _{(1 + 100)} (100 ℃)
= 26) 100 parts by weight of SRF (carbon filler) 7
Parts by weight, MTC (carbon filler) 8 parts by weight, triazine CH ₂ = CFCF ₂ OCF (CF ₃ ) C obtained in Example 1
N8.5 parts by weight and perhexa-2,5-B2 part
Knead with an inch rubber roll, and JSR CULARAS
The vulcanization curve was measured at 160 ° C. using TOMETER IIF. For comparison, CH ₂ = CFCF ₂ OCF (CF ₃ ) C
The components were kneaded in the same manner as above, except that 3 parts by weight of TAIC was used instead of N.

Each of the kneaded materials was press-vulcanized at 160 ° C. for 10 minutes to obtain a sheet having a thickness of 2 mm, and subjected to secondary vulcanization at 200 ° C. for 4 hours. The normal physical properties (strength at break and elongation) of the vulcanized sheet were measured using ORIENTC TENSILON according to JIS K6301. The vulcanized sheet produced in the same manner was heat-aged in a 250 ° C. oven for 70 hours, and the aging properties were measured. Table 2 shows the results.

[0035]

[Table 2]

[Brief description of the drawings]

FIG. 1 is an IR chart of a product obtained in Example 1.

FIG. 2 is an IR chart of the product obtained in Example 2.

FIG. 3 is an IR chart of a product obtained in Example 10.

Claims (5)

[Claims] 1. A general _{formula: CH 2 = CFCF 2 O- (} CF 2 O) x - (CF 2 CF 2 O) y - (CX 1 2 CF 2 CF 2 O) z - (CFX 2
CF ₂ O) _w -CFX ³ -CN (wherein X ¹ is a hydrogen atom, a fluorine atom or a chlorine atom, X ² is a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group, X ³ is a hydrogen atom, Represents a fluorine atom, a chlorine atom or a trifluoromethyl group, x, y, z and w each independently represent a number of 0 to 20, provided that
The sum of x, y, z and w does not exceed 20. ) A fluorine-containing nitrile represented by the formula: 2. CH ₂ ＣＦCFCF ₂ O—CF (CF ₃ ) —C
_{N, CH 2 = CFCF 2 O} -CF (CF 3) CF 2 0-CF (C
F ₃₎ -CN or _{CH 2 = CFCF 2 O- [CF} (CF 3) CF 2 0] 2 -CF (C
F ₃₎ a fluorine-containing nitrile according to claim 1 is -CN. 3. A compound of the general formula: (Wherein, Rf is the formula _{:-( CF 2 O) x - (} CF 2 CF 2 O) y - (CX 1 2 CF 2 CF
₂ O) _z- (CFX ² CF ₂ O) _w -CFX ^3- (where X ¹ X ² X ³ xyz and w are as defined above). A) a fluorine-containing polyfunctional triazine compound represented by the formula: 4. The molecular weight is from 1,000 to 1,000,000.
The fluorinated nitrile polymer according to claim 1, wherein 5. A compound having a molecular weight of 1,000 to 1,000,000.
The copolymer of fluorinated nitrile and another copolymerizable monomer according to claim 1 or 2, wherein the content of fluorinated nitrile is 0.1 to 99 mol%.