JP2000247914A - Fluorine-containing diene compound, polymer therefrom and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fluorine-containing diene compound, its polymer and a method for producing them. SOLUTION: A fluorine-containing diene compound expressed by the formula: RfCF=CHCH=CH2 (wherein, Rf is a 1-11C polyfluoroalkyl group) is obtained by the dehydrofluorination reaction of a fluorine-containing olefin expressed by the formula RfCF2CH2CH=CH2 or RfCFCH=CHCH3 in the presence of a basic compound. A polymer obtained from the fluorine-containing diene compound is excellent in heat resistance, oil resistance, water repellency or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluorine-containing conjugated diene compound, a method for producing the same, and a polymer thereof and a method for producing the same.

[0002]

2. Description of the Related Art A perfluorodiene compound having double bonds at both ends of a molecule has low polymerization reactivity, and can be polymerized under special conditions to obtain a cyclized polymer or a partially three-dimensional polymer. Are known (LA Wall, Flu)
oro Polymer, Wiley-Intersc
ence, 4, High Pressure Pol
ymization, p. 127). It is also known that a fluorine-containing compound having two types of double bonds having different reactivities undergoes cyclopolymerization to obtain an amorphous fluorine-containing polymer (JP-A-63-238115, JP-A-63-238115). 63-23
8111).

Many reports have been made on fluorinated butadiene. For example, as for perfluorobutadiene, a polymer having a relatively low molecular weight can be obtained in low yield only by anionic polymerization. Also, many compounds in which several hydrogen atoms of butadiene are substituted with fluorine atoms are known, and their polymers are also known (US Pat. No. 2,915,508). Although this polymer of fluorinated butadiene can be used as an elastomer, it has insufficient heat resistance, oil resistance, water repellency, etc. due to the low content of fluorine atoms.

However, no conjugated butadiene compound having a substituent having a relatively large number of carbon atoms is known, and in particular, a butadiene compound having a fluorine-containing substituent is not known. Also, these polymers are not known. Further, as a polymer having a fluoroalkyl group, particularly a fluoroalkyl group having a relatively large number of carbon atoms in a side chain, only a fluoroalkyl group-containing acrylate polymer and a fluoroalkyl group-containing silicone polymer are known, An olefin polymer containing a so-called fluorine-containing substituent having a large number of carbon atoms is not known.

[0005]

SUMMARY OF THE INVENTION The present invention provides a novel fluorine-containing conjugated diene compound having a fluoroalkyl group as a substituent, a method for producing the same, and a polymer of the fluorine-containing conjugated diene compound and a method for producing the same. Aim.
Since the polymer of the present invention has a fluoroalkyl group as a substituent, the fluorine content in the polymer is high, and the polymer is excellent in heat resistance, oil resistance, water repellency and the like.

[0006]

The present invention relates to a fluorine-containing diene compound represented by the formula 1 (hereinafter referred to as a fluorine-containing diene compound (formula 1), wherein R ^f is a polyfluoroalkyl having 1 to 11 carbon atoms). Represents a group). R ^f CF = CHCH = CH ₂ Formula 1 In addition, a fluorine-containing olefin represented by Formula 2 (hereinafter, referred to as a fluorine-containing olefin (Formula 2)) or a fluorine-containing olefin represented by Formula 3 (hereinafter, including fluorine-containing olefin) Provided is a method for producing a fluorine-containing diene compound (Formula 1), which comprises subjecting a fluoroolefin (Formula 3) to a deHF reaction in the presence of a basic compound. R ^f CF ₂ CH ₂ CH = CH ₂ Formula 2 R ^f CF ₂ CH = CHCH ₃ Formula 3

Further, a repeating unit represented by Formula 4 (hereinafter referred to as a repeating unit (Formula 4)) and / or Formula 5
(Hereinafter, a repeating unit (formula 5)
And a polymer having a molecular weight of 5 × 10 ³ to 1 × 10 ⁷ (where R ^f represents a polyfluoroalkyl group having 1 to 11 carbon atoms). The present invention also provides a method for producing the above polymer, which comprises subjecting a fluorine-containing diene compound (Formula 1) to radical polymerization.

[0008]

Embedded image —CH ₂ CH = CHCFR ^f − Formula 4

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing diene compound (formula 1) of the present invention is a conjugated compound and has a double bond at the 1-position and the 3-position. R ^f in Formulas 1 to 5 has 1 to 1 carbon atoms.
1 polyfluoroalkyl group. When the carbon number of the polyfluoroalkyl group is 12 or more, the solubility of the fluorine-containing diene compound in an organic solvent is reduced, so that the synthesis becomes difficult, and the reaction activity of the fluorine-containing diene compound in polymerization tends to be reduced.

As the polyfluoroalkyl group, the number of hydrogen atoms in the corresponding alkyl group is 60 to 100.
%, Preferably 80 to 100%, is a polyfluoroalkyl group substituted with a fluorine atom. Further, some or all of the remaining hydrogen atoms may be substituted with halogen atoms other than fluorine atoms such as chlorine atoms.

When the polyfluoroalkyl group has 3 or more carbon atoms, the polyfluoroalkyl group may be branched or linear. More preferred polyfluoroalkyl groups are linear polyfluoroalkyl groups. The perfluoroalkyl group having 3 to 9 carbon atoms is preferable as the polyfluoroalkyl group because the fluorine content in the polymer increases and the heat resistance, oil resistance, water repellency and the like of the polymer are improved. Further, a linear perfluoroalkyl group is preferred.

The fluorine-containing diene compound of the present invention (formula 1)
Can be used to remove fluorinated olefin (formula 2) or fluorinated olefin (formula 3) in the presence of a basic compound.
It can be produced by reacting.

The fluorine-containing olefin (formula 2) is represented by R ^f CF
After the allyl halide or allyl acetate, such as allyl chloride in ₂ I was added radically obtained by treatment such as zinc. Instead of allyl acetate, allyl alcohol is added, then acetylated, and then treated with zinc. Alternatively, it is obtained by radically adding methanol to R ^f CF ₂ CH ＝ CH ₂ , followed by acetylation, and then deacetic acid. The fluorinated olefin (formula 3) can be obtained by adding propylene to R ^f CF ₂ I and removing HI with a basic compound.

The reaction between the fluorinated olefin (formula 2) or the fluorinated olefin (formula 3) and the basic compound may be carried out in a homogeneous system using isopropyl alcohol (hereinafter referred to as IPA) as a solvent or in a solvent such as water or methanol. It proceeds in a heterogeneous system. In heterogeneous reactions, a phase transfer catalyst such as an alkyl ammonium salt is used. In general, high conversion and selectivity can be obtained in a homogeneous reaction.
In particular, it is preferable to use IPA as a solvent.

Examples of the basic compound include alkali metal hydroxides such as potassium hydroxide (hereinafter referred to as KOH) and sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, and tert-butoxy. An alkali metal alkoxide such as potassium (hereinafter, referred to as t-BuOK) or an organic amine compound such as triethylamine or pyridine is used.

In view of the conversion of the reactants and the selectivity of the product, KOH,
Sodium hydroxide is preferably used. In the reaction with the fluorinated olefin (Formula 3), the fluorinated olefin (Formula 3) has a relatively low reactivity and thus has a relatively basic t-type.
BuOK is preferably used. In the case of a fluorine-containing olefin (formula 2), the reaction temperature is usually preferably in the range of 40 to 100C. In the case of a fluorine-containing olefin (formula 3), 40
The range of -150 ° C is preferred.

Further, the fluorine-containing diene compound (formula 1) of the present invention is obtained by adding allyl alcohol to R ^f CF ₂ I, reducing iodine as an adduct, and halogenating a hydroxyl group with hydrogen bromide or the like. Thereafter, it is obtained by reacting with a basic compound and dehalogenating with dehydrogen fluoride, dehydrobromide or the like in a one-step reaction.

The fluorine-containing diene compound (formula 1) of the present invention has high polymerizability, and a polymer having polymerized units based on the fluorine-containing diene compound (formula 1) can be obtained. The polymer of the present invention has at least a repeating unit (Formula 4) and / or a repeating unit (Formula 5). Repeating unit (Equation 4)
Is a structure in which a fluorine-containing diene compound (formula 1) is polymerized in a 1,4-polymerization mode, and a repeating unit (formula 5) has 1,
2- A structure polymerized in a polymerization mode.

The polymer of the present invention has a molecular weight of 5 × 10 ³ -1.
× 10 ⁷ . If it is larger than 1 × 10 ^7, it becomes difficult to produce a polymer. If it is smaller than 5 × 10 ³ , the polymer has low thermal stability and is easily decomposed. Further, the polymer of the present invention may include a repeating unit based on another monomer in addition to the repeating unit (Formula 4) and the repeating unit (Formula 5).

Other monomers include fluorinated olefins such as tetrafluoroethylene (hereinafter referred to as TFE), chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride and hexafluoropropylene, and hydrocarbons such as ethylene and propylene. Olefin, methyl (meth)
Acrylic compounds such as (meth) acrylates such as acrylates and fluoroalkyl (meth) acrylates and (meth) acrylonitrile; styrene and its derivatives; Preferred other monomers are fluorinated olefins. The proportion of the repeating units based on other monomers in the polymer was 50 mol% based on all repeating units.
The following is preferred.

The polymer of the present invention can be obtained by various polymerization methods such as ionic polymerization and radical polymerization. It is preferable to obtain a polymer by a radical polymerization method capable of performing polymerization under particularly mild conditions using a radical initiator. The polymerization is bulk polymerization,
Polymerization modes such as solution polymerization, suspension polymerization, and emulsion polymerization can be employed.

As the radical initiator, a water-soluble initiator or an oil-soluble initiator is selected and used according to the polymerization mode. The polymer of the present invention can be polymerized using a general radical initiator. For example, in emulsion polymerization, water-soluble peroxides such as potassium persulfate, ammonium persulfate, and disuccinic peroxide are used. In the case of suspension polymerization, solution polymerization, or bulk polymerization, non-fluorinated peroxides such as diisopropyl peroxydicarbonate (hereinafter referred to as IPP) and benzoyl peroxide, and fluorine-based peroxides such as perfluorobutanoic acid peroxide are also used. Product, azobisisobutyronitrile (hereinafter referred to as AIB
An azo compound such as N) is used.

In the solution polymerization, CCl is used as a solvent.
Fluorine-based solvents such as F ₂ CF ₂ CHClF (hereinafter referred to as HCFC225cb), F (CF ₂ ) ₈ F, and H (CF ₂ ) ₆ F are preferably used. The polymerization temperature is preferably from 50 to 100 ° C. for radical polymerization.

The polymer of the present invention has heat resistance, water repellency, and flexibility by having a polyfluoroalkyl group.
Excellent oil resistance. Since it is soluble in a fluorine-based solvent, it is useful as a paint or coating material having excellent weather resistance, water repellency, and non-adhesion. Also has a high fluorine content,
It has a low dielectric constant and is useful as a low dielectric constant coating.

Further, the polymer has a double bond,
Since crosslinking reaction and functional group introduction can be easily performed, it is also useful as a comonomer for modifying general-purpose resins such as polybutadiene, nitrile rubber, and styrene-butadiene copolymer. Can be easily introduced into coalescence.

[0026]

EXAMPLES Example 1 (Reference Example) Synthesis of 3- (perfluorooctyl) propene In a 2 L three-necked flask equipped with a stirrer, Dimroth, and dropping funnel, 2 kg of perfluorooctyl iodide, AIB
N20g, allyl acetate 44 at 70 ° C under nitrogen.
0 g was added dropwise over 6 hours. At 5 and 10 hours after the start of the dropwise addition, 20 g of AIBN was further added, and the mixture was reacted for 15 hours to obtain an allyl acetate adduct.

300 g of zinc powder and 500 mL of methanol
Allyl acetate adduct was added dropwise to another flask containing the mixture while maintaining the reflux temperature of methanol, and the reaction was continued for 1 hour after completion of the addition. After the reaction, the reaction product of the lower phase separation was distilled under reduced pressure, 3- (perfluorooctyl) propene _{[C 8 F 17 CH 2 CH} = CH 2, boiling point 68.5 ° C. / 20
torr] 1340 g. The yield was 79.5%.

Example 2 Synthesis of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene 165 g of KOH and 500 ml of IPA were placed in a 2 L three-necked flask equipped with a stirrer, Dimroth, and dropping funnel.
Under stirring, 3- (perfluorooctyl) propene 920
g was added dropwise. Since the reaction generates heat, the reaction solution was slowly dropped over about 1 hour, and then the reaction was continued at 70 ° C. for 2 hours.

Thereafter, IPA was extracted from the reaction product by extraction with water and distilled under reduced pressure to obtain 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene [C ₇ F ₁₅ CF =
CHCH = CH ₂ , boiling point 65.5 ° C./20 torr] 6
77.8 g were obtained. The yield was 77.0%. ¹⁹ F-
According to NMR, 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene was a mixture of a cis-form and a trans-form, and the cis-form / trans-form ratio was about 1/9.

¹⁹ F-NMR (solvent: CD ₃ COCD ₃ )
δ (ppm): - 81 ( 3F, CF 3 -), - 115.
5 (0.1F, -CF = CH- (cis)), -118
_{(2F, CF 3 -C F 2} -), - 122~124 (8
_{F, -CF 2 -), -} 126.5 (2F, -C F 2 -C
F =), -130.5 (0.9F, -CF = CH- (t
rans)), ¹ H-NMR (solvent: CD ₃ COCD ₃ ) δ (pp
m): 5.48~5.76 (2H, CH 2 =), 6.4
3-6.81 (2H, = CH-CH =).

Example 3 (Reference Example) Synthesis of 1- (perfluorooctyl) propene 1 kg of perfluorooctyl iodide and 30 g of AIBN were placed in a 2 L stainless steel autoclave, followed by purging with nitrogen.
0.5 kg of propylene was injected, and the temperature was raised to 80 ° C. 7
At 0 ° C., propylene was added up to 5 kg / cm ² G. As the reaction proceeded, propylene was added in order to keep the pressure constant. The reaction continued until the pressure drop almost disappeared. Thereafter, the mixture was cooled and unreacted propylene was purged to obtain a propylene adduct.

2 with stirrer, Dim funnel, dropping funnel
L in a three-necked flask, 200 g KOH and 5 methanol
Then, the resulting propylene adduct was added dropwise with stirring. The lower-layer reaction product after phase separation was distilled, and 1-
(Perfluorooctyl) propene [C ₈ F ₁₇ CH = C
HCH ₃ , boiling point 91.7 ° C./50 torr] 756 g was obtained. The yield was 89.7%.

Example 4 Synthesis of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene In a 500 mL three-necked flask equipped with a stirrer, a Dim funnel and a dropping funnel, 40 g of t-BuOK and tert- Butyl alcohol (hereinafter referred to as t-BuOH) 500 m
92 g of L, 1- (perfluorooctyl) propene was added, and the mixture was stirred at 150 ° C. for 2 hours. Thereafter, t-BuOH was extracted from the reaction product with water, removed, and distilled under reduced pressure to obtain 1-fluoro-. 1- (perfluoroheptyl) pig-1,3-diene _{[C 7 F 15 CF = CHCH} =
CH ₂ ] 53 g was obtained. The yield was 60.2%.

Example 5 (Reference Example) Synthesis of 3- (perfluorohexyl) propene 1870 g of perfluorohexyl iodide was placed in a 2 L three-necked flask equipped with a stirrer, Dimroth, and dropping funnel.
20 g of AIBN was added, and 545 g of allyl acetate was added dropwise at 70 ° C. under nitrogen over 6 hours. 5, from the start of dripping
At the 10th hour, 20 g each of AIBN was further added and reacted for 15 hours to obtain an allyl acetate adduct.

352 g of zinc powder and 800 mL of methanol
The resulting allyl acetate adduct was added dropwise to another flask containing the mixture at the reflux temperature of methanol, and the reaction was continued for 1 hour after the completion of the addition. After the reaction, the reaction product in the lower layer after phase separation was distilled under reduced pressure to give 3- (perfluorohexyl) propene [C ₆
F ₁₃ CH ₂ CH = CH ₂ , boiling point 74 ° C./125 torr
r] 1058.3 g. The yield was 70.1%.

Example 6 Synthesis of 1-fluoro-1- (perfluoropentyl) buta-1,3-diene In a 500 mL three-necked flask equipped with a stirrer, Dimroth, and dropping funnel, 84 g of KOH and 80 mL of IPA were placed.
3- (Perfluorohexyl) propene 360 under stirring
g was added dropwise. Since the reaction generates heat, the reaction solution was slowly dropped over about 1 hour, and then the reaction was continued at 70 ° C. for 2 hours.

Thereafter, IPA was extracted from the reaction product by extraction with water and distilled under reduced pressure to give 1-fluoro-1- (perfluoropentyl) buta-1,3-diene [C ₅ F ₁₁ CF = C
HCH = CH ₂ , boiling point 59.3 ° C./70 torr] 29
4.8 g were obtained. The yield was 86.7%. ¹⁹ F-N
According to MR, 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene was a mixture of a cis-form and a trans-form, and the cis-form / trans-form ratio was about 1/9.

¹⁹ F-NMR (solvent: CD ₃ COCD ₃ )
δ (ppm): - 81 ( 3F, CF 3 -), - 114.
5 (0.1F, -CF = CH- (cis)), -117
_{(2F, CF 3 -C F 2} -), - 123 (4F, -CF
_{2 -), - 126 (2F} , -C F 2 -CF =), - 13
0.5 (0.9F, -CF = CH- (trans)), ¹ H-NMR (solvent: CD ₃ COCD ₃ ) δ (pp
m): 5.4~5.9 (2H, CH 2 =), 6.2~
7.0 (2H, = CH-CH =).

Example 7 (Reference Example) Synthesis of 3- (perfluorobutyl) propene In a 2 L three-necked flask equipped with a stirrer, a Dim funnel and a dropping funnel, 1962 g of perfluorobutyl iodide, A
20 g of IBN was added, and 681 g of allyl acetate was added dropwise at 70 ° C. under nitrogen over 6 hours. 5, 1 from the start of dripping
At time 0, 20 g of AIBN was additionally added, and the mixture was reacted for 15 hours to obtain an allyl acetate adduct.

415 g of zinc powder and 800 mL of methanol
The resulting allyl acetate adduct was added dropwise to another flask containing the mixture at the reflux temperature of methanol, and then the reaction was continued for 1 hour. After the reaction, the reaction product in the lower layer after phase separation was distilled under reduced pressure to give 3- (perfluorobutyl) propene [C ₄ F ₉
CH ₂ CH = CH ₂ , boiling point 81.8 ° C.] 998 g was obtained. The yield was 97.6%.

Example 8 Synthesis of 1-fluoro-1- (perfluoropropyl) buta-1,3-diene In a 500 mL three-necked flask equipped with a stirrer, a Dim funnel, and a dropping funnel, 126 g of KOH and 80 mL of IPA were placed. Under stirring, 3- (perfluorobutyl) propene 39
0 g was added dropwise. Since the reaction generates heat, the solution was slowly dropped over about 1 hour, and the reaction was continued at 70 ° C. for 2 hours.

Thereafter, IPA was extracted from the reaction product by extraction with water and distilled under reduced pressure to obtain 1-fluoro-1.
-(Perfluoropropyl) buta-1,3-diene [C
_{3 F 7 CF = CHCH = CH} 2, boiling point 81.2 ° C.] 23
8.5 g were obtained. The yield was 66.2%. ¹⁹ F-N
According to MR, 1-fluoro-1- (perfluoropropyl) buta-1,3-diene was a mixture of a cis-form and a trans-form, and the cis-form / trans-form ratio was about 1/9.

¹⁹ F-NMR (solvent: CD ₃ COCD ₃ )
δ (ppm): - 81 ( 3F, CF 3 -), - 115.
5 (0.1F, -CF = CH- (cis)), -118
_{(2F, CF 3 -C F 2} -), - 127.5 (2F, -
_{C F 2 -CF =), -} 130.5 (0.9F, -CF =
CH- (trans)), ¹ H-NMR (solvent: CD ₃ COCD ₃ ) δ (pp
m): 5.4~5.9 (2H, CH 2 =), 6.2~
7.0 (2H, = CH-CH =).

Example 9 Polymerization of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene 20 g of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene in a 50 mL flask And IPP0.
3 g was added, and polymerization was carried out at 50 ° C. for 24 hours under a nitrogen stream. After the polymerization, unreacted monomers were distilled off under reduced pressure.
After dissolving in 5 cb and adding IPA to precipitate and purifying,
Drying under reduced pressure at 60 ° C. for 12 hours gave 9.6 g of a polymer.
The polymerization yield was 48%.

The polymer was gum-like and soluble in a fluorine-based solvent, and swelled in a ketone-based solvent such as acetone. Since it was soluble in a fluorine-based solvent and had no gel component, it was found that three-dimensional crosslinking did not occur during polymerization. The obtained polymer was an amorphous polymer having a glass transition temperature of 8 ° C, and had a 10% by weight heat loss temperature in air of 294 ° C.

The molecular weight in terms of polymethyl methacrylate (hereinafter referred to as M _n ) by GPC using HCFC225cb as a solvent
Was about 19,500. In addition, ¹⁹ F-NMR
, That the peak derived from = CF- had disappeared,
Since a peak of -174 ppm derived from> CF- is observed, and a peak derived from> CH- is not observed in ¹³ C-NMR, the polymer is composed of only the 1,4-polymerization mode. I understood. The obtained polymer was cast on a glass plate, and the contact angle with water was measured. As a result, it was 104 °, indicating high water repellency.

¹⁹ F-NMR (solvent: CCl ₂ FCClF
₂ / CD ₃ COCD ₃ = 1/1 (weight ratio) mixed solvent) δ
(Ppm): - 81 (3F , CF 3 -), - 118 (2
_{F, CF 3 -C F 2 -} ), - 122~-127 (10
F, -CF ₂ -, _{and> CF-C F 2 -)} , - 174
(1F,> CF-).

Example 10 Polymerization of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene 20 g of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene in a 50 mL flask And AIBN
0.3 g was added, and polymerization was carried out at 80 ° C. for 24 hours under a nitrogen stream. After polymerization, unreacted monomers are distilled off under reduced pressure, and HCFC
After dissolving in 225 cb and purifying by adding IPA to precipitate, the residue was dried under reduced pressure at 60 ° C. for 12 hours to obtain 15.8 g of a polymer. The polymerization yield was 79%. HCFC225cb
The M _n by GPC with a solvent was about 77,900.

Example 11 Polymerization of 1-fluoro-1- (perfluoropentyl) buta-1,3-diene 20 g of 1-fluoro-1- (perfluoropentyl) buta-1,3-diene in a 50 mL flask And IPP0.
3 g was added, and polymerization was carried out at 50 ° C. for 24 hours under a nitrogen stream. After the polymerization, unreacted monomers were distilled off under reduced pressure.
After dissolving in 5 cb and adding IPA to precipitate and purifying,
It was dried under reduced pressure at 60 ° C. for 12 hours to obtain 13.3 g of a polymer. The polymerization yield was 66.6%. The polymer was syrupy, soluble in a fluorine-based solvent, and swollen in a ketone-based solvent such as acetone.

It was found that three-dimensional cross-linking did not occur during the polymerization, since it was soluble in the fluorine-based solvent and had no gel component. The resulting polymer was an amorphous polymer having a glass transition temperature of 8 ° C., a 10% by weight heat loss temperature in air of 304 ° C., and _Mn of about 9800.

Further, in ¹⁹ F-NMR, the peak derived from = CF- disappeared, and the peak derived from> CF-
Observation of peak at 174 ppm, ¹³ C-NMR
No peak derived from> CH- was observed, indicating that the polymer was composed of only the 1,4-polymerization mode. Cast the obtained polymer on a glass plate,
When the contact angle with water was measured, it was 102 degrees, indicating high water repellency.

¹⁹ F-NMR (solvent: CCl ₂ FCClF
₂ / CD ₃ COCD ₃ = 1/1 (weight ratio) mixed solvent) δ
(Ppm): - 81 (3F , CF 3 -), - 117 (2
_{F, CF 3 -C F 2 -} ), - 123~126 (6F, -
CF ₂ -, _{and> CF-C F 2 -)} , - 174 (1
F,> CF-).

Example 12 Polymerization of 1-fluoro-1- (perfluoropropyl) buta-1,3-diene 20 g of 1-fluoro-1- (perfluoropropyl) buta-1,3-diene in a 50 mL flask. And IPP0.
3 g was added, and polymerization was carried out at 50 ° C. for 24 hours under a nitrogen stream. After the polymerization, unreacted monomers were distilled off under reduced pressure.
After dissolving in 5 cb and adding IPA to precipitate and purifying,
Drying under reduced pressure at 60 ° C. for 12 hours gave 8.8 g of a polymer.
The polymerization yield was 44%. The polymer was syrupy, soluble in a fluorine-based solvent, and swollen in a ketone-based solvent such as acetone.

Since it was soluble in a fluorine-based solvent and had no gel component, it was found that three-dimensional crosslinking had not occurred during the polymerization. The obtained polymer is an amorphous polymer having a glass transition temperature of 8 ° C., and a 10% by weight heat loss temperature in air of 296.
° C and _Mn was about 7700.

Also, in ¹⁹ F-NMR, the peak derived from = CF- disappeared, and the peak derived from> CF-
Observation of peak at 174 ppm, ¹³ C-NMR
No peak derived from> CH- was observed, indicating that the polymer was composed of only the 1,4-polymerization mode. Cast the obtained polymer on a glass plate,
When the contact angle with water was measured, it was 97 degrees, indicating high water repellency.

¹⁹ F-NMR (solvent: CCl ₂ FCClF
₂ / CD ₃ COCD ₃ = 1/1 (weight ratio) mixed solvent) δ
(Ppm): - 81 (3F , CF 3 -), - 118 (2
_{F, CF 3 -C F 2 -} ), - 128 (2F, -CF 2
-, and _{-C F 2 -CF <), -} 174 (1F,> C
F-).

Example 13 Copolymerization of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene with TFE 1-fluoro-1- (perfluoroheptyl) butamate was placed in a 200 mL stainless steel autoclave. 20 g of 1,3-diene, 20 g of H (CF ₂ ) ₆ F, and 0.4 g of an initiator (Perloyl IB, manufactured by NOF Corporation) were charged, and TFE was added.
After replacing the inside of the reactor with TFE, TFE was injected under pressure such that the pressure of TFE at 80 ° C. became 8 kg / cm ² G, and polymerization was carried out with stirring for 24 hours. After that, purge TFE,
After IPA was added for precipitation and purification, the residue was dried under reduced pressure at 60 ° C. for 12 hours to obtain 7.6 g of a polymer.

The composition of this polymer determined by total fluorine analysis was 1-fluoro-1- (perfluoroheptyl).
We are repeating units based on a repeating unit / TFE-based buta-1,3-diene = 96/4 (molar ratio), M _n
Was about 17100.

Example 14 Copolymerization of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene and methyl acrylate 1-fluoro-1- (perfluoroheptyl) buta-1 in a 50 mL flask , 3-diene, 15 g of methyl acrylate and 0.3 g of IPP were added, and polymerization was carried out at 50 ° C. for 24 hours under a nitrogen stream. After the polymerization, unreacted monomers were distilled off under reduced pressure and dissolved in HCFC225cb.
A mixed solvent of PA / methanol (1/1 by weight) was added for precipitation and purification, followed by drying under reduced pressure at 60 ° C. for 12 hours to obtain 12.8 g of a polymer. The polymerization yield was 70.7%.

The polymer was syrupy, soluble in a fluorine-based solvent, and swollen in a ketone-based solvent such as acetone. Also,
It was found that IPA having no solubility in the homopolymer of the fluorinated diene compound swelled and the copolymerization proceeded.

The composition of this polymer determined by total fluorine analysis was 1-fluoro-1- (perfluoroheptyl).
The repeating unit based on buta-1,3-diene / the repeating unit based on methyl acrylate = 58/42 (molar ratio), and _Mn was about 11,100.

Example 15 Copolymerization of 1-fluoro-1- (perfluoroheptyl) buta-1,3-diene with styrene 1-fluoro-1- (perfluoroheptyl) buta-1, butane-1 37 g of 3-diene, 8.8 g of styrene, 25 g of HCFC225cb, and IPP
0.3 g was added, and polymerization was carried out at 50 ° C. for 5 hours under a nitrogen stream. After the polymerization, unreacted monomers were distilled off under reduced pressure, and HCFC2
The solution was dissolved in 25 cb, purified by precipitation by adding a mixed solvent of IPA / methanol (1/1 by weight), and dried under reduced pressure at 60 ° C. for 12 hours to obtain 11.5 g of a polymer. The polymerization yield was 25.1%. The polymer was solid.

The composition of this polymer determined by total fluorine analysis was 1-fluoro-1- (perfluoroheptyl).
The repeating unit based on buta-1,3-diene / the repeating unit based on styrene = 60/40 (molar ratio);
_Mn was about 11100.

[0064]

The polymer of a fluorine-containing diene compound having a polyfluoroalkyl group as a substituent has a high fluorine content and is excellent in heat resistance, oil resistance, water repellency and the like.

Claims (4)

[Claims] Equation 1
(Wherein, R ^f represents a polyfluoroalkyl group having 1 to 11 carbon atoms). R ^f CF = CHCH = CH ₂ Formula 1 2. The fluorine-containing diene compound according to claim 1, wherein the fluorine-containing olefin represented by the formula 2 or the fluorine-containing olefin represented by the formula 3 is subjected to a deHF reaction in the presence of a basic compound. Manufacturing method. R ^f CF ₂ CH ₂ CH = CH ₂ Formula 2 R ^f CF ₂ CH = CHCH ₃ Formula 3 3. A polymer containing a repeating unit represented by the formula 4 and / or a repeating unit represented by the formula 5, and having a molecular weight of 5 × 1.
A polymer having a number of 0 ³ to 1 × 10 ⁷ (where R ^f represents a polyfluoroalkyl group having 1 to 11 carbon atoms). Embedded image —CH ₂ CH = CHCFR ^f − Formula 4 4. The method according to claim 3, wherein the fluorine-containing diene compound according to claim 1 is subjected to radical polymerization.