JP4039079B2 - Fluorine-containing diene compound, process for producing the same, and polymer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel fluorine-containing diene compound, a production method thereof and a polymer.
[0002]
[Prior art]
As for the fluorine-containing diene compound, R ^f CF═CHCH═CH ₂ described in JP-A No. 2000-247914 is known. The polymer obtained using the fluorine-containing diene compound is excellent in water repellency and oil repellency. However, in order to obtain a compound as a raw material, a catalyst such as zinc, which is difficult to handle, is used. It was necessary to go through the reaction.
[0003]
[Problems to be solved by the invention]
The present invention solves the aforementioned drawbacks of the prior art. That is, an object of the present invention is to provide a fluorine-containing diene compound that can be produced without using a catalyst such as zinc, which is difficult to handle, or without going through a multistage reaction. Another object is to provide a method for producing the fluorine-containing diene compound and a polymer.
[0004]
[Means for Solving the Problems]
The present invention provides a fluorine-containing diene compound represented by R ^f CH═CFCH═CH ₂ (hereinafter referred to as compound 1). In the present specification, R ^f represents a C 1-12 polyfluoroalkyl group (hereinafter referred to as R ^f group).
[0005]
The present invention relates to a compound represented by R ^f CH ₂ CF ₂ CH ₂ CH ₂ X (where X represents an iodine atom, the same shall apply hereinafter) (hereinafter referred to as compound 2) as a basic compound. The present invention provides a method for producing Compound 1 in which deHX reaction and deHF reaction are performed in the presence of
[0006]
The _invention, -CH 2 CH = CFCHR ^f - represented by the repeating units (. Hereinafter referred to as repeating unit A) and / or ^{_{-CH 2 CH (CF = CHR f}} ) - repeating units (hereinafter represented by And a repeating unit B.), and a polymer having a mass average molecular weight of 2 × 10 ^{3 to} 5 × 10 ⁶ .
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the R ^f group is preferably a group in which 60% or more of hydrogen atoms in the corresponding alkyl group are substituted with fluorine atoms, and particularly preferably a group in which 80% or more is substituted with fluorine atoms. Further, some or all of the remaining hydrogen atoms may be substituted with other halogen atoms such as chlorine atoms.
[0008]
When the number of carbon atoms in the R ^f group is 3 or more, the R ^f group may be branched or linear, and is preferably linear. The number of carbon atoms in the R ^f group is preferably 4 to 10 because the content of fluorine atoms in the polymer can be increased and the heat resistance, oil resistance, water repellency and the like of the polymer can be improved.
[0009]
Compound 1 of the present invention is preferably produced by subjecting Compound 2 to a deHX reaction and a deHF reaction in the presence of a basic compound. For example, compound 1 is obtained by subjecting compound 2 to de-HX reaction in the presence of a basic compound to give a compound represented by R ^f CH ₂ CF ₂ CH═CH ₂ (hereinafter referred to as compound 3), and further basic. It is preferably produced by deHF reaction in the presence of the compound.
[0010]
Compound 2 is obtained by adding vinylidene fluoride and ethylene to the compound represented by R ^f -X by radical reaction. In the radical reaction, it is preferable to add ethylene after adding vinylidene fluoride.
[0011]
The reaction between compound 2 and the basic compound is preferably carried out in the presence of a solvent. Preferred examples of the solvent include tert-butanol (hereinafter referred to as t-BuOH), methanol (hereinafter referred to as MeOH), water and the like. In particular, t-BuOH is preferable.
[0012]
As the basic compound, an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal alkoxide, an organic amine compound, or the like is preferably used. Specifically, potassium hydroxide (hereinafter referred to as KOH), sodium hydroxide, calcium hydroxide, magnesium hydroxide, tert-butoxypotassium (hereinafter referred to as t-BuOK), triethylamine, pyridine and the like are preferable. .
[0013]
The basic compound is preferably t-BuOK in the reaction with the compound 2 from the viewpoint of the reaction rate, the selectivity of the product, etc., and the reaction with the compound 3 is preferably KOH having a relatively weak basicity. In addition, the reaction may be performed by adding a phase transfer catalyst. Preferred examples of the phase transfer catalyst include alkyl ammonium salts.
In the deHX reaction and the deHF reaction in the presence of a basic compound, the reaction temperature is preferably 40 to 100 ° C., and the reaction time is preferably 1 to 100 hours.
[0014]
The compound 1 of the present invention has high polymerizability, and a polymer having a polymer unit based on the compound 1 is obtained. The polymer of the present invention preferably has the repeating unit A and / or the repeating unit B, and has a mass average molecular weight of 2 × 10 ^{3 to} 5 × 10 ⁶ . When the mass average molecular weight is too large, it is difficult to produce the polymer, and when it is too small, the thermal stability of the polymer is lowered and the polymer is easily decomposed.
[0015]
The repeating unit A has a structure in which the compound 1 is polymerized in a 1,4-polymerization mode, and the repeating unit B has a structure in which the compound 1 is polymerized in a 1,2-polymerization mode. The polymer of the present invention may be a polymer containing both the repeating unit A and the repeating unit B, or may be a polymer containing only the repeating unit A or only the repeating unit B.
[0016]
The polymer of this invention may contain the repeating unit based on another monomer other than said repeating unit. Other monomers include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, ethylene, propylene, methyl (meth) acrylate, fluoroalkyl (meth) acrylate, (meth) acrylonitrile Preferred examples include saturated hydrocarbon group-containing (meth) acrylates having 14 or more carbon atoms, styrene and derivatives thereof. In particular, a saturated hydrocarbon group-containing (meth) acrylate having 14 or more carbon atoms is preferred. In the polymer, the proportion of repeating units based on other monomers is preferably 90 mol% or less.
[0017]
The polymer of the present invention can be obtained using a polymerization method such as an ionic polymerization method or a radical polymerization method. In the present invention, it is preferable to obtain a polymer by using a radical polymerization method that can be polymerized under a particularly mild condition using a radical initiator. Specifically, polymerization methods such as suspension polymerization, solution polymerization, bulk polymerization, and emulsion polymerization can be preferably employed.
[0018]
As the radical initiator, a water-soluble initiator or an oil-soluble initiator can be used depending on the polymerization method. For example, in emulsion polymerization, a water-soluble peroxide is preferably used, and for example, potassium persulfate, ammonium persulfate, disuccinic acid peroxide and the like are preferably used. In suspension polymerization, solution polymerization or bulk polymerization, non-fluorine peroxide, fluorine peroxide, and azo compound are preferably used. For example, diisopropyl peroxydicarbonate, benzoyl peroxide, perfluorobutanoic acid peroxide, Azobisisobutyronitrile (hereinafter referred to as AIBN) and the like are preferably used.
[0019]
In the solution polymerization, a fluorine-based solvent such as Cl (CF ₂ ) ₂ CHClF, F (CF ₂ ) ₈ F, H (CF ₂ ) ₆ F is preferably used as the solvent. The reaction temperature for obtaining the polymer is preferably 50 to 100 ° C. in radical polymerization.
[0020]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these.
[0021]
[Example 1]
In a 1 L three-necked flask equipped with a stirrer, Dimroth and dropping funnel, 200 g of 3,3,5,5,6,7,7,8,8,8-undecafluoro-1-iodooctane and MeOH A solution prepared by dissolving 28 g of KOH in 150 g of MeOH was added dropwise at room temperature over 1 hour.
[0022]
Thereafter, the mixture was heated to reflux, and after 3 hours from the start of reflux, a solution prepared by dissolving 11 g of KOH in 80 g of MeOH was added, and further reacted for 5 hours. After the reaction, the resulting reaction mixture containing C ₄ F ₉ CH ₂ CF ₂ CH═CH ₂ was washed with distilled water to obtain a reaction solution.
[0023]
143 g of the obtained reaction solution and 50 g of t-BuOH were placed in a 1 L three-necked flask equipped with a stirrer, a Dimroth, and a dropping funnel, and 39 g of t-BuOK and tetrabutylammonium (hereinafter referred to as TBAB). A solution prepared by dissolving 11 g in 150 g of t-BuOH was added dropwise at room temperature over 1 hour.
[0024]
Thereafter, the mixture was heated to reflux, and 12 hours after the start of reflux, a solution in which 20 g of t-BuOK was dissolved in 100 g of t-BuOH was added, and the mixture was further reacted for 4 hours. After the reaction, the obtained reaction crude liquid was washed with distilled water and distilled under reduced pressure to obtain 23 g (formation of C ₄ F ₉ CH═CFCH═CH ₂ (boiling point 65 ° C./200 torr) which is the target product 1 The isolated yield of product 1 was 17%.). The obtained product 1 was only a trans form. The measurement results of ¹⁹ F-NMR and ¹ H-NMR are shown.
[0025]
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.8 (3F, CF ₃ —), −107.9 (2F, —CF ₂ —CH═), −108.4 (1F, − CH = CF- (trans)), - 124.9~-126.3 (4F, -CF 2 -).
[0026]
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 5.01 (1H, —CH═CF—), 5.55-5.93 (2H, CH ₂ =), 6.16 (1H, = CF-CH =).
[0027]
[Example 2]
3, 3, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-pentadecafluoro-into a 1 L three-necked flask equipped with a stirrer, Dimroth, and dropping funnel 400 g of 1-iododecane and 200 g of MeOH were added, and a solution in which 47 g of KOH was dissolved in 200 g of MeOH was added dropwise at room temperature over 1 hour.
[0028]
Thereafter, the mixture was heated to reflux, and after 3 hours from the start of reflux, a solution in which 12 g of KOH was dissolved in 100 g of MeOH was added, and further reacted for 5 hours. After the reaction, the resulting reaction mixture containing C ₆ F ₁₃ CH ₂ CF ₂ CH═CH ₂ was washed with distilled water to obtain a reaction solution.
[0029]
Into a 1 L three-necked flask equipped with a stirrer, Dimroth and dropping funnel, 298 g of the obtained reaction solution and 100 g of t-BuOH were put, and 60 g of t-BuOK and 17 g of TBAB were dissolved in 250 g of t-BuOH. The solution was added dropwise at room temperature over 1 hour.
[0030]
Thereafter, the mixture was heated to reflux, and after 12 hours from the start of reflux, a solution prepared by dissolving 45 g of t-BuOK in 200 g of t-BuOH was added, and further reacted for 8 hours. After the reaction, the obtained reaction crude liquid was washed with distilled water and distilled under reduced pressure to obtain 65 g of the desired product ₂ (C ₆ F ₁₃ CH═CFCH═CH ₂ (boiling point 66 ° C./30 torr)) The isolated yield of product 2 was 23%.). The product obtained was only the trans isomer. The measurement results of ¹⁹ F-NMR and ¹ H-NMR are shown.
[0031]
¹⁹ F-NMR (solvent: CDCl ₃ ) δ (ppm): −81.5 (3F, CF ₃ —), −107.6 (2F, —CF ₂ —CH═), −108.4 (1F, − CH = CF- (trans)), - 122.1~126.5 (8F, -CF 2 -),
(Solvent: CDCl ₃ ) δ (ppm): 5.01 (1H, —CH═CF—), 5.55-5.93 (2H, CH ₂ =), 6.15 (1H, ═CF—CH═) ).
[0032]
[Example 3]
In a 100 mL glass ampule, 9 g of product 1, 51 g of AK-225 (trade name, manufactured by Asahi Glass Co., Ltd.) and 0.36 g of AIBN were added, and freeze deaeration was repeated three times using liquid nitrogen. A polymerization reaction was carried out at 65 ° C. for 12 hours to obtain a polymer. When the solution after completion of the reaction was analyzed by gas chromatography, the unreacted product 1 was not substantially detected. The obtained polymer had a mass average molecular weight of 9,300, and the ratio of the repeating unit A to the repeating unit B in the polymer was about 1: 1.
[0033]
Distilled water was added to the solution containing the polymer to dilute the polymer to a concentration of 5% by mass to obtain a test solution. 1 mL of the test solution was dropped on a 7 cm square glass plate, spin-coated at 3000 rpm for 30 seconds, and then cured at 110 ° C. for 1 hour to prepare a sample. The contact angle with respect to water of the surface of the obtained sample was 110.4 degrees, and the contact angle with respect to hexadecane was 68.5 degrees.
[0034]
[Example 4]
A polymerization reaction was carried out in the same manner as in Example 3 except that the product 2 was used instead of the product 1. The obtained polymer had a mass average molecular weight of 10,300, and the ratio of the repeating unit A to the repeating unit B in the polymer was about 1: 1. Further, a sample was produced in the same manner as in Example 3. The contact angle with respect to water of the surface of the obtained sample was 109 degrees, and the contact angle with hexadecane was 66.7 degrees.
[0035]
[Example 5]
In a 100 mL glass polymer ampoule, 8.11 g of product 1, 12.25 g of stearyl acrylate, 0.42 g of hydroxyethyl acrylate, 0.3 g of polyoxyalkylene glycol monomethacrylate, 1. of polyoxyethylene octylphenyl ether. 68 g, 0.42 g of stearyl triethylammonium chloride, 26.20 g of water, 10.5 g of acetone, 0.11 g of stearyl mercaptan as a molecular weight regulator, 2,2′-azobis (2-methylpropionamidine) as an initiator 0.04 g of dihydrochloride was added.
[0036]
The emulsion was purged with nitrogen and subjected to a polymerization reaction at 55 ° C. for 12 hours to obtain an emulsion having a solid content concentration of 38.4% by mass. The weight average molecular weight of the obtained polymer was 45800, and the ratio of polymerized units based on the product 1 in the polymer was 39.9 mol%.
[0037]
3 g of the obtained emulsion was dropped into 27 g of methanol to precipitate a polymer. The obtained polymer was vacuum-dried at 30 ° C. overnight, and then a solution having a polymer concentration of 5% by mass was obtained using AK-225.
[0038]
A sample was prepared in the same manner as in Example 3 using the obtained solution. The contact angle with respect to water of the surface of the obtained sample was 107.2 degrees, and the contact angle with hexadecane was 66.7 degrees.
[0039]
[Example 6]
A polymerization reaction was carried out in the same manner as in Example 5 except that the product 2 was used in place of the product 1, and an emulsion having a solid content concentration of 39.1% by mass was obtained. The weight average molecular weight of the obtained polymer was 47000, and the ratio of polymerized units based on the product 2 in the polymer was 33.1 mol%.
[0040]
Further, a sample was produced in the same manner as in Example 5. The obtained sample had a contact angle with water of 109.4 degrees and a contact angle with hexadecane of 69.4 degrees.
[0041]
【The invention's effect】
The fluorine-containing diene compound of the present invention is a novel compound. The compound can be synthesized without using a catalyst such as zinc, which is difficult to handle, and without going through a multistage reaction. Moreover, this compound is excellent in polymerizability, and can obtain a polymer with a large mass average molecular weight.
[0042]
The polymer of the present invention is excellent in flexibility, and has excellent heat resistance, water repellency and oil repellency by having an R ^f group. Further, since a fluorine atom is bonded to a carbon atom having a double bond, it is thermally stable. Further, since the polymer is soluble in a fluorine-based solvent, it is useful as a paint or coating material excellent in weather resistance, water repellency and non-adhesiveness. Furthermore, since it contains a large amount of fluorine atoms, it has a low dielectric constant and is useful for applications as a low dielectric constant film.
[0043]
Further, since the polymer of the present invention has a double bond, it can further undergo a crosslinking reaction, and a functional group can be easily introduced into the polymer. Furthermore, ^Rf groups can be easily introduced into resins such as polybutadiene, nitrile rubber, styrene / butadiene copolymer, and the resin can be easily modified.

Claims (3)

_{^{R f CH = CFCH = CH 2}} ( provided that, ^{R f} represents a polyfluoroalkyl group having 1 to 12 carbon atoms.) Fluorinated diene compound represented by the. R ^f CH ₂ CF ₂ CH ₂ CH ₂ X (where R ^f represents a polyfluoroalkyl group having 1 to 12 carbon atoms and X represents an iodine atom) A method for producing the above-mentioned fluorine-containing diene compound, characterized by performing a de-HX reaction and a de-HF reaction below. -CH ₂ CH = CFCHR ^f - repeating units represented by and / or ^{_{-CH 2 CH (CF = CHR f}} ) - comprises a repeating unit represented by, and the weight average molecular weight of 2 × ¹⁰ 3 ~5 × ^{10 6.} A polymer. However, ^Rf shows a C1-C12 polyfluoroalkyl group.