JPS62153236A - Vinyl compound containing perfluoroalkenyloxy group - Google Patents

Abstract

NEW MATERIAL:A vinyl compound bearing perfluoroalkenyloxy group of the formula (R is H, CH3; n is 2-4; the benzene nucleus is substituted in the p-, m- or o-position). EXAMPLE:p-perfluorohexenyloxyvinylbenzene. USE:Polymerizable monomer. Elimination of the perfluoro-substituent by hydroly sis hardly occurs and the functions of the additives are maintained for a long period of time, when it is used in rubber material, a releasing agent, water repellent, oil repellent, optical materials, gas-separation membrane material, resist material, paper processing agent or fiber-finishing agent. PREPARATION:For example, hexafluoropropene oligomers are used as the starting substance to effect the reaction with a halogen-substituted phenol such as p-chlorophenol in the presence of a tertiary amine at 6-150 deg.C. Then, the resultant ether is allowed to react with a Grignard reagent of a vinyl halide such as vinyl chloride to give the compound of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel perfluoroalkenyloxy group-containing vinyl compound useful as a polymerizable monomer or the like.

[Conventional technology and its problems]

Conventionally, as a vinyl compound having a perfluoro substituent, OH,=OH-0-0f(2(OF, JIOF.

(In the formula, %l represents an integer of 3 to 12) 01, I, =OH-0000820H, (OF27m
OF.

(In the formula, m represents an integer of 3 to 12.) etc. are known. However, the former known compound is
(It is difficult to copolymerize with general-purpose monomers such as methanoacrylic acid ester, styrene monomer, acrylonitrile, etc.), and there are significant restrictions on the polymerization method and copolymerization composition. The use of these compounds has been severely limited due to the drawbacks that they are easily separated and difficult to maintain the desired function over a long period of time.

[Means for solving problems]

The present inventors have made extensive studies to overcome the above-mentioned defects in polymerizable compounds having perfluoro substituents, and have found that they have excellent polymerizability and can be used as raw materials for homopolymers or copolymers, and that they can be perfluorinated by hydrolysis, etc. There is almost no separation of the fluoro substituent, and the function can be maintained for a long time, making it suitable for rubber materials, mold release agents, water and oil repellents, optical materials,
Gas separation membrane materials, resist materials, antifouling paints, paper processing agents,
ε provides fluorine-containing polymers useful as fiber treatment materials, etc.
We have discovered a new perfluoroalkenyloxy group-containing vinyl compound that can.

That is, the novel perfluoroalkenyloxy group-containing vinyl compound according to the present invention has the general formula It is a compound represented by [indicating ortho position].

The novel perfluoroalkenyloxy group-containing vinyl compound according to the present invention is disclosed in, for example, JP-A-50-117705.
Using the hexafluoropropene oligomer disclosed in the above publication as a raw material, the reaction temperature was 0 to 150°C in the presence of a halogeno-substituted phenol such as P-chlorophenol, 0-chlorophenol, or p-7'lomophenol and a tertiary amine.
By reacting with methiperfluoroalkenyl halogen-substituted phenyl ether and further Grignard reaction with a vinyl halide such as vinyl chloride, alkyl or the hexafluoroglopene oligomer ethyl (or isopropylnophenol) is reacted. It can be obtained by obtaining perfluoroalkenyl ethyl (or isopropylnophenyl ether) and subjecting it to a dehydrogenation reaction in the presence of a catalyst such as recycled iron. Alternatively, it can also be obtained by a method in which a reaction is carried out with [impropenyl]phenol (para, meta or ortho) in the presence of a tertiary amine at a reaction temperature of D to 100°C.

The novel perfluoroalkenyloxy group-containing vinyl compound according to the present invention is useful as a polymerizable monomer.

The polymerization may be in any form such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, photopolymerization, or radiation polymerization, and the polymerization method may be either radical polymerization or ionic polymerization.

This novel perfluoroalkenyloxy group-containing vinyl compound can be homopolymerized or copolymerized with other polymerizable monomers depending on the purpose. Examples of other polymerizable monomers include acrylic acid, methacrylic acid, and esters thereof. , styrene/, styrenic monomers such as α-methylstyrene, acrylamide, methacrylamide, N-
Acrylamide monomers such as methylacrylamide,
Acrylonitrile, methacrylonitrile, vinyl acetate,
Examples include vinyl alkyl ketones, maleino acid, fumaric acid, their esters, vinyl chloride, vinyl fluoride, vinyliso-7 monomers such as vinylizo 7 fluoride, butadiene monomers such as butadiene, isoprene, chloroprene, etc. It is not limited to compounds.

Furthermore, in the polymer containing the novel perfluoroalkenyloxy group-containing vinyl compound according to the present invention, the perfluoro substituent of the new compound is chemically and physically very stable, and is resistant to hydrolysis and light. Since the removal of perfluoro substituents due to etc. hardly occurs, the desired function can be maintained for a long period of time, and the novel perfluoroalkenyloxy group-containing vinyl compound of the present invention is an extremely useful compound. .

(Example) Next, the present invention will be explained in detail using examples.

Example 1 p-perfluorohexenyloxyvinylbenzene (p
-c,p,,oa6n,ax■=ar-f2) synthesis:
5 equipped with a stirrer, thermometer, reflux condenser, and dropping funnel.
In a 00ml four-bottle flask, p-chlorophenol 19
．． 28,! 9 (0.15 molp, hexafluoropropene 2 t isomerization as a solvent in the presence of fluoride ions, o 1 g (0
, 15 mol) and 2 oomg of dimethyl sulfoxide were added. Triethylamine 15.18I (0.15 mol) was added to the dropping funnel while stirring and mixing at a reaction temperature of 20 to 30"C.
was added gradually. The reaction was allowed to proceed for about 3 hours, and completion of the reaction was confirmed by gas chromatography. The reaction product was poured into water, and the lower layer was separated and washed with dilute hydrochloric acid and water. This crude product was distilled under reduced pressure with a boiling point of 695~
p-perfluorohexenyloxychlorobenzene 5 B-969 (yield q 6.2
%) Got it:.

Elemental analysis measurements: O: 35.1%, H: 0.8%, F: 5t5
懺OjJ: 8.8chi Calculated value: O:! 15.27%, n:o, 99chi, F:5
1, 15 Chi 0/: 8.68% Infrared absorption spectroscopy Based on benzene nucleus (absorption 6.2 μ, 6.7 μ Absorption based on 0-F 74-93 μ (broad absorption) Prepare a 500 ml four-loaf flask, 2.44 g (0.1 gram atom) of p-perfluorohexenyloxychloropenze/40.86.j9 synthesized above was added and the reaction vessel was heated to 40°C.
(0.1 mol) was dissolved in 200 ml of tetrahydrofuran, dried, and then transferred to a dropping funnel. 20ml of this solution
1, 2 ml of ethyl bromide was added to start the reaction. The above solution was gradually added dropwise over 2 hours under reflux to react.

Subsequently, while maintaining the reaction mixture at 15° C., 12.5 g of molded vinyl was blown into the reaction mixture through a blowing tube for 1 hour to cause a reaction. Dilute hydrochloric acid was added to this reaction mixture for hydrolysis, and then the organic layer was separated. This organic! - After removing the solvent,
Boiling point 76-75℃/'l 5 Audience 11 by vacuum distillation
p-berfluorohexenyloxyvinylbenzene of i was obtained.

Elemental analysis measurement value: O: 41. s%, H: 1.6 yen, F:
52.4 coefficient calculation value: O: 42.02chi, H: 1.76%
, F: 52, 22 Infrared absorption spectrum analysis Based on benzene nucleus (absorption 6.3 μ, 6.7 μ) Absorption based on 0-F 7.4-94 μ (I hotbed absorption) Based on vinyl group (absorption 6.1 μ) Example 2 p-perfluorononenyloxyisopropenylbenzene (p-0, F17006) 1.0 (OH3) = 014
] Synthesis: Equipped with a stirrer, thermometer, reflux condenser, and dropping funnel.
- In a 500 ml four-bottle flask, Φsafluoropropene trimer 72.01 (0.16 molp, p.
-isopropenylphenol 20.13.9 (0,1
5 mol] and 200 ml of N,N-dimethylformamide were added. 4u 4rl at reaction temperature 40-50℃! While mixing, add 15.18 g of triethylamine (
0.15 mol was added gradually.

The reaction was completed in about 2 hours. Pour the reaction product into water, separate the lower layer and wash with dilute hydrochloric acid and water. The crude product was distilled under reduced pressure to a boiling point of 83.5-b1, 5 mtlHji
, <-Fluorononenyloxyisopropenylbenzene (p-c, F1700.lN40 (Oll, J=
CI-12)77i6! i (yield 91.4%) was obtained.

Elemental analysis measurements: O: 38.1%, H: 1.5%, F: 57.
4% calculated value: O: 38.32%, H: 1.61 yen, F
:57, 24% Infrared absorption spectrum analysis Based on benzene nucleus (absorption 6.2μ, 6.7μ0-
Based on F (absorption 7.4-94μ (broad absorption)) based on inpropenyl group <M 6.Dμ Example 6 Homopolymerization of p-perfluorohexenyloxyvinylbenzene: p- obtained in Example 1 Perfluorohexenyloxyvinylpenzeno [p -06F, 0061 (40H=
OH2] 32.02 g (0.08 mol) was dissolved in methyl isobutyl keto y15ami, 0.32 g (0.002 mol) of azobisisobutyronitrile was added as a polymerization initiator, and the mixture was heated at a temperature of 80°C under a nitrogen atmosphere. Polymerization was carried out for 5 hours. The resulting reaction mixture was taken up in petroleum ether.

The precipitate was filtered and dried to obtain 31.41 g of white powder (
A yield of 97.1%) was obtained.

Further, the above white powder was dissolved in methyl isobutyl ketone, applied to a galvanized steel plate, and then heated and dried. This coated steel plate was immersed in slightly alkaline warm water (60°C) for 300 hours. As a result of peeling off the coating film of the test steel plate and conducting elemental analysis, it was found that the P content was 51.5% (measured value before the immersion test, the F content was 5%).
1.8]).

As mentioned above, this new perfluoroalkenyl vinyl compound had excellent polymerizability, and the perfluoro substituent of the compound was difficult to eliminate by hydrolysis or the like (and had extremely harsh properties).

Comparative Example 1 1.1-dihydroundecylfluorohexyl vinyl ether (OH,=OH-0-OH,O,!lF1.:
) 65.22 ji (0,2 mol and methyl methacrylate 2o, o2ji (0,2 mol and butyl acetate 2[
]Om/, 0.859 (o,oos morph) of azobisisobutyronitrile was added as a polymerization initiator, and polymerization was carried out at a temperature of 80°C for 7 hours in a nitrogen atmosphere.The resulting reaction mixture was dissolved in petroleum The mixture was poured into ether, and the precipitate was filtered and dried.

When the above precipitate was subjected to elemental analysis, no fluorine atoms were detected. From this, it was found that the above two types of vinyl compounds hardly copolymerized.

Comparative Example 2 1.1.2.2-tetrahydrotridecylfluorooctyl acrylate (an
Polymerization was carried out in the same manner as in Example 6, except that 2=OH-0000)120H20,F,3] was used. The resulting reaction mixture was poured into petroleum ether, and the precipitate was filtered and dried.

The above precipitate was dissolved in methyl isobutyl ketone, coated on a galvanized steel plate, and then dried by heating.

This painted steel plate was soaked in slightly alkaline hot water (60"C) for 300 minutes.
Soaked for an hour. The coating film of the test steel plate was peeled off and elemental analysis was performed, and the result was that the F content was 25.8% (measured value before the immersion test: F content 1i - 58.7%), and the perfluoro substituents were significantly removed. I found out that

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydrogen or a methyl group, n is an integer from 2 to 4,
A perfluoroalkenyloxy group-containing vinyl compound represented by (the position of the benzene nucleus substituent is para, meta or ortho position).