JP2001247497A - Perfluorodecalyl group-containing peroxide, perfluorodecalyl group-containing compound and their production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new perfluoro-organic peroxide useful as a polymerization initiator and a specific perfluoro-organic group-incorporating agent, and a new perfluoro-organic compound obtained by using the above peroxide. SOLUTION: This peroxide of the formula: RfC(=O)OO(O=)CRf (I) (wherein, Rf is 1-perfluorodecalyl group and/or 2-perfluorodecalyl group) is produced by reacting a perfluorodecalin carboxylic acid halide with a prescribed peroxide, and the perfluoro-organic compound is produced by reacting the peroxide of formula (I) with a prescribed monomer or aromatic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel peroxide containing a perfluorodecalyl group, its use, a compound containing a perfluorodecalyl group obtained by using the peroxide, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, various compounds having a perfluoroalkyl group have been known.
For example, perfluoroalkanoyl peroxide is widely used as a polymerization catalyst for a fluorine-based monomer. As such an organic peroxide, for example, perfluoroalkanoyl peroxide is known as a catalyst for copolymerizing tetrafluoroethylene and hexafluoropropene (JP-A-49-10290).

In addition, stable compounds containing a perfluoroalkyl group have attracted attention in recent years because they exhibit useful properties such as weather resistance, light resistance, water / oil repellency, and physiological activity. In particular, a perfluoroalkyl group-containing polymer has low surface tension, low refractive index, low reflectivity, heat resistance,
It has excellent properties such as cold resistance, oil resistance, electrical insulation, water repellency, oil repellency, antifogging property, antifouling property, mold release property, chemical resistance, lubricity etc. Used in the fields of surface treatment agents, fiber treatment agents, surfactants, paints, wax additives, mold release agents, etc., especially glassware, optical lenses, eyeglass lenses, intraocular lenses, plastic fibers, separations It is considered to be useful as a surface treatment agent for imparting water repellency, oil repellency, antifouling property, irregular reflection prevention property, etc. to the surface of films, medical materials and the like.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel perfluoroorganic peroxide useful as a polymerization initiator for a specific monomer or a specific perfluoroorganic group-introducing agent, and a novel perfluoroorganic peroxide. An object of the present invention is to provide a novel perfluoro organic compound obtained by using an oxide.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on novel perfluoro organic compounds, and as a result,
The present inventors have found that an organic peroxide having a perfluorodecalyl group, and various novel perfluorodecalyl group-containing compounds obtained using the same can be suitable for the purpose. Reached.

That is, the present invention provides a compound represented by the general formula: RfC (（O) OO (O）) CRf (I) wherein Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group. The present invention provides a perfluorodecalyl group-containing peroxide represented by the formula:

This peroxide is a novel compound which has not been described in the literature and has the general formula RfC (（O) X (where Rf is a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group, Represents a halogen atom), and is reacted with at least one selected from hydrogen peroxide, sodium peroxide, potassium peroxide and barium peroxide.

This peroxide is rich in reactivity and has various properties and uses. Particularly, a polymerization initiator for a monomer having an ethylenic polymerizable group containing the peroxide as an active ingredient, and a perfluorodeca containing the peroxide. Useful as a rill group introducing agent.

Further, the present invention provides various perfluorodecalyl group-containing compounds represented by the following general formulas (II) to (IV) using such a peroxide. Rf- (A) m- (B) n-Rf (II) wherein Rf is a 1-perfluorodecalyl group and / or 2-perfluorodecalyl group, and A and B are different ethylenic polymer groups. M and n are 0
~ 5000 (where m + n ≠ 0)] Ar-Rf (III) (wherein, Ar is a non-polymerizable aromatic compound residue, and Rf is a 1-perfluorodecalyl group and / or 2 -
(Ar′-H) x (Ar′-Rf) y (IV) (where Ar ′ is a polymerizable aromatic monomer unit residue, bonded to a carbon atom of an aromatic ring by a perfluorodecalyl group) Rf is bonded to a carbon atom of the aromatic ring by a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group, x is an integer of 0 to 10000, and y is 1 to 10000
Is an integer of

[0010] These perfluorodecalyl group-containing compounds are novel compounds which have not been published in any literature, and can be produced as follows. The perfluorodecalyl group-containing compound of the general formula (II) of the present invention is obtained by converting a monomer having one or more ethylenic polymerizable groups into a compound represented by the general formula RfC (＝ O) OO (O ＝) CRf (wherein Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group). In addition, the perfluorodecalyl group-containing compound of the general formula (III) of the present invention is a compound represented by the general formula: Ar-H (wherein, Ar is a non-polymerizable aromatic compound residue, and its bond is aromatic. An aromatic compound represented by the general formula RfC (＝ O) OO (O ＝) CRf (wherein Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group) It can be produced by reacting with the represented perfluorodecalyl group-containing peroxide. Further, the perfluorodecalyl group-containing compound of the general formula (IV) of the present invention has a general formula Ar ″ —H (wherein, Ar ″ is a polymerizable aromatic monomer residue, and its bonding hand is A polymerizable aromatic monomer represented by the following formula: RfC (= O) OO (O =) CRf (where Rf is a 1-perfluorodecalyl group and / or 2-perfluorodecalyl) The compound can be produced by reacting with a perfluorodecalyl group-containing peroxide represented by the following formula:

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the perfluorodecalyl group-containing peroxide represented by the above formula (I) of the present invention (hereinafter also referred to as peroxide (I)), Rf in the formula is 1-perfluorodecalyl. Group and / or 2-perfluorodecalyl group, in other words, one or both of the 1-perfluorodecalyl group and 2-perfluorodecalyl group, and in other words, 1-perfluorodecalyl group and 2-perfluorodecalyl group. And the peroxide (I) can also be referred to as perfluorodecalin carbonyl peroxide. Peroxide (I)
Among them, bis (perfluorodecalin-1-carbonyl) peroxide in which Rf is a 1-perfluorodecalyl group is preferable because it is easily available.

The peroxide (I), ie perfluorodecalin carbonyl peroxide, is a corresponding acid halide (eg perfluorodecalin carboxylic acid fluoride, perfluorodecalin carboxylic acid chloride, perfluorodecalin carboxylic acid bromide, perfluorodecalin carboxylic acid iodide) ) Can be used as the starting compound to produce the compound by the following method. The first method involves reacting the acid halide with hydrogen peroxide, preferably in alkaline conditions, such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, The reaction is performed in the presence of an alkali component such as potassium carbonate or a mixture thereof. The preferred dose ratio of the other component to the acid halide is in the range of 0.3 to 20, especially 0.5 to 10 for hydrogen peroxide, and 0.3 to 10, especially 0.5 to 7 for the alkali component. Is chosen. If this ratio exceeds 20 with hydrogen peroxide or exceeds 10 with an alkali component, the yield of peroxide (I) as a target decreases, and if the ratio becomes less than 0.3 with hydrogen peroxide. If the content of the alkali component is less than 0.3, the reaction time tends to be long and the yield tends to decrease. A second method is to convert the acid halide to sodium peroxide,
It reacts with at least one inorganic peroxide selected from potassium peroxide and barium peroxide.
The preferred dose ratio of the inorganic peroxide to the acid halide is selected in the range of 0.3 to 20, especially 0.5 to 15, in molar ratio. If this ratio exceeds 20, the yield of the desired peroxide (I) decreases, and if it is less than 0.3, the reaction time becomes longer and the yield tends to decrease. The alkali component and the inorganic peroxide used in these methods are preferably used as an aqueous solution, and the concentration is preferably 1 to 60% by weight, more preferably 5 to 30% by weight. If the concentration exceeds 60% by weight, the yield of the desired peroxide (I) decreases, and if it is less than 1% by weight, the reaction time becomes longer and the yield tends to decrease.

[0013] The reaction conditions in these methods vary depending on the type of various raw materials, the proportions used, and the like.
Usually, normal pressure is used as the pressure, and the reaction temperature is -30 to 50.
C, preferably in the range of -20 to 10C. If the reaction temperature is lower than -30 ° C, the reaction time becomes longer,
On the other hand, if the temperature exceeds 50 ° C., it is not preferable because control of the reaction system (reaction operation) becomes difficult, for example, the pressure during the reaction becomes too high. The reaction time is usually selected in the range of 0.5 to 20 hours, but it is desirable to set conditions so that it is practically 0.5 to 10 hours.

In these methods, it is preferable to use an organic solvent capable of dissolving the acid halide corresponding to the peroxide (I). As such organic solvents, halogenated aliphatic solvents and halogenated aromatic solvents are particularly preferred. Specifically, for example, methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, , 1
-Difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,
1,3-tetrachlorotetrafluoropropane, 1,
1,1-trichloropentafluoropropane, 1,1,
2-trichlorotrifluoroethane, 1,1,1,2,2
2-pentafluoro-3,3-dichloropropane, 1,
Examples thereof include 1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride, hexafluoroxylene, and pentafluorobenzene, and particularly, industrially, 1,1,2-trichlorotrifluoro Ethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride,
Alternatively, a mixed solvent obtained by mixing these at an arbitrary ratio [for example, AK-225 (1,1,1,2,2-pentafluoro-3,3-dichloropropane and 1,1,1 manufactured by Asahi Glass Co., Ltd.)
A mixed solvent with 2,2,3-pentafluoro-1,3-dichloropropane)].

The peroxide (I) of the present invention, ie, perfluorodecalin carbonyl peroxide, has a perfluorodecalyl group and therefore has a 10-hour selected half-life temperature lower than that of ordinary fluorine-based organic peroxides. And a monomer having a group having an α, β-ethylenically unsaturated bond such as a vinyl group, an alkyl-substituted product thereof, or a halogen-substituted product thereof, particularly a monomer having the following general formula (VI) ) And the polymerization initiator of the monomer of the general formula (VII), particularly, a radical polymerization initiator.

Then, such a monomer is used alone or in combination of two or more.
A compound having a perfluorodecalyl group at both terminals, preferably a homopolymer or copolymer, usually represented by the general formula (II), which is reacted with perfluorodecalin carbonyl peroxide and preferably further polymerized, is preferably used. Can be produced. At this time, a compound having a perfluorodecalyl group at one end may be by-produced.

Among the compounds of the general formula (II),
Has the general formula Rf- (CH_TwoCR¹R^Two) M- (CH_TwoCR^ThreeR^Four) N-Rf (V) wherein Rf is a 1-perfluorodecalyl group and / or
A 2-perfluorodecalyl group is represented by R¹And R^ThreeAre the same
Hydrogen atoms or alkyl groups which are or different from each other
And R^TwoAnd R^FourAre different from each other,
Group, 1-pyrrolidinyl group, halogen atom, cyano group,
-SiR^aR^a'R^a″ (Where R^a, R^a', R^a″ Is the same
One or different carbon atoms having 1 to 10 carbon atoms.
Alkyl group, alkoxy group or alkano having 1 to 4 carbon atoms
Represents an yloxy group, a halogen atom, or a hydrogen atom),
-CO_TwoR^FiveOr -CONR⁶R⁷[Where R^Five, R⁶, R
⁷Are the same or different from each other,
It may have a cycloalkyl group having a prime number of 1 to 18.
Alkyl group, cycloalkyl group, glycidyl group, -D-
Q (where D is a urethane bond, an ester bond, an amide
Bond, oxygen atom or nitrogen atom optionally intervening
Q is an isocyanate group (-NCO)
Or a blocked isocyanate group),-
(Y¹)_a− (Y ^Two-O)_b-R⁸[Where Y¹, Y^TwoAre the same
Or alkyls having 1 to 6 carbon atoms which are different from each other
Rene group is represented by R⁸Is a hydrogen atom, an alkyl group or -SiR^bR
^b'R^b″ (Where R^b, R^b', R^b″ Are the same
Or an alkyl group, an alkoxy group,
Represents a hydrogen atom, an alkanoyloxy group or a hydrogen atom
A) is 0 or 1, b is an integer of 0 to 20
Or hydroxyalkyl having 1 to 20 carbon atoms
Group, aminoalkyl group, alkylaminoalkyl group or
Dialkylaminoalkyl groups or their ammonium
Salt, cyanoalkyl group, alkylthioalkyl group,
Kilphosphonium group, phosphoalkyl group, or glycidyl
And R represents an alkyl group.⁶And R⁷Are each other
To form a heterocycle with N to which they are attached
May be used], -OCOR^Five(Where R^FiveIs the same as above
Taste) or -Y¹-(O-Y^Two)_b-R⁹(here
And Y¹, Y^TwoAre the same or different, charcoal
R 1 represents an alkylene group having a prime number of 1 to 6⁹Is hydroxyl or alcohol
A xy group, b represents an integer of 0 to 20),
m and n are each 0 to 5000 (however, m + n ≠ 0)
(Hereinafter, also referred to as compound P)
Is preferred.

In the symbols in the above formula (V), the alkylene group of Y ^{1 is} an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group or a trimethylene group, and the alkylene group of Y ² is preferably an ethylene group, a propylene group, respectively, wherein _{^{:-( Y 1) a - (Y}} 2 -
The group represented by _{^{O) b -R 8 -SiR b R}} b 'R b "
^{And, -Y 1 -SiR b R b '} R b " _{^{and, - (Y 2 -O) d}} -R
⁸ (where d is an integer of 1 to 20), among which a poly (oxyethylene) group, a poly (oxypropylene) group or a poly (mixed oxyethylene-oxypropylene) group or a terminal hydroxyl group thereof is represented by —OSiR ^b R ^b ′ R ^b ″ or a group substituted with an alkoxy group has the formula: —Y ¹ — (O—Y ² ) _b —
As the group represented by R ⁹ , Y ¹ is a methylene group, and the residue is a poly (oxyethylene) group, a poly (oxypropylene) group or a poly (mixed oxyethylene-oxypropylene) group, or a terminal hydroxyl group thereof. Are preferably each substituted with an alkoxy group.

The group represented by the formula: -DQ is a saturated hydrocarbon group substituted with an isocyanate group, which may have a urethane bond, an oxygen atom or a nitrogen atom,
The isocyanate group is blocked with an isocyanate blocking agent, and the divalent saturated hydrocarbon group in D is preferably an alkylene group, and such a divalent saturated hydrocarbon group has a urethane bond, an oxygen atom or a nitrogen atom interposed. Or an isocyanatoalkyl group or a blocked isocyanatoalkyl group, especially an isocyanatoalkyl group or an isocyanatoalkylaminocarbonyloxyalkyl group (for example, a compound represented by the formula: —CH ₂ CH ₂ —O—CO—NHCH ₂ CH ₂ NCO And the like, and those obtained by blocking them.

Isocyanate blocking agents which act on free isocyanate groups to suppress their reactivity,
For example, those which react with isocyanate groups to eliminate free isocyanate groups. Under appropriate conditions, for example, under heating conditions or in the presence of a catalyst, isocyanate groups are generated to restore the reactivity of isocyanate groups. The compound is not particularly limited as long as it causes the reaction. Preferably, a phenol-based, alcohol-based, imine-based, oxime-based, lactam-based or active methylene-based compound having an active hydrogen group is used.

[0021] In ^{addition, -SiR a R a 'R a} " and -SiR ^b R
^b 'The R ^b ", for example organosilanes, organohalogen silanes, organo silanols, organoalkoxysilane, organosiloxane, organosilicon esters, residues of the organic silicon compound such as organo silazane and the like, among which an organosilyl group , An organohalogenosilyl group and an organosiloxy group are preferred.

Compound P has the general formula CH_Two= CR¹R^Two (VI) and CH_Two= CR^ThreeR^Four (VII) 中 wherein, R¹And R^ThreeAre the same or different
A hydrogen atom or an alkyl group^TwoAnd R^FourAre different from each other
A piperidino group, 1-pyrrolidinyl
Group, halogen atom, cyano group, -SiR^aR^a'R^a″
(Where R^a, R^a', R^a″ Is the same or
C1-C10 alkyl groups different from each other, C1
To 4, an alkoxy group or an alkanoyloxy group, a halo
Gen atom or hydrogen atom), -CO_TwoR^FiveOr -C
ONR⁶R⁷[Where R^Five, R⁶, R⁷Are the same
Or a hydrogen atom, a C1-18
An alkyl group optionally having a cycloalkyl group,
Alkyl group, glycidyl group, -DQ (where D is
Rethane bond, ester bond, amide bond, oxygen atom or
A divalent saturated hydrocarbon group optionally interposed by a nitrogen atom,
Q is an isocyanate group (-NCO) or
Each represents a cyanate group),-(Y¹)_a− (Y ^Two−
O)_b-R⁸[Where Y¹, Y^TwoAre the same or
A different alkylene group having 1 to 6 carbon atoms is represented by R⁸Is
Hydrogen atom, alkyl group or -SiR^bR^b'R^b"(here
And R^b, R^b', R^b″ Are the same or
Different, alkyl, alkoxy, halogen,
A represents a lucanoyloxy group or a hydrogen atom), a is 0 or
1, b represents an integer of 0 to 20], or carbon
Hydroxyalkyl group, aminoalkyl of formulas 1 to 20
Group, alkylaminoalkyl group or dialkylamino group
Alkyl group or their ammonium salts, cyanoalkyl
Group, alkylthioalkyl group, alkylphosphonium
Group, a phosphoalkyl group, or a glycidylalkyl group.
And R⁶And R⁷Are connected to each other
May form a heterocyclic ring with the N to which they are bonded.]
COR^Five(Where R^FiveHas the same meaning as above)
Is -Y¹-(O-Y^Two)_b-R⁹(Where Y¹, Y^TwoAre the same
Or alkyls having 1 to 6 carbon atoms which are different from each other
Rene group is represented by R⁹Represents a hydroxyl group or an alkoxy group, and b represents 0 to
20 represents an integer of 20).
And at least one selected from the monomers represented by the general formula: RfC (= O) OO (O =) CRf (where Rf is a 1-perfluorodecalyl group and / or
Represents a 2-perfluorodecalyl group)
By reacting with a fluorodecalyl group-containing peroxide
Can be manufactured.

As the monomer of the general formula (VI) or the general formula (VII) used in the method for producing the compound P, vinyl monomers, especially (meth) acrylic acid or acid derivatives such as esters and amides thereof are preferable. As the (meth) acrylate type vinyl monomer, those having a free isocyanate group are also used. However, in order to extend the pot life and to improve the ease of handling by using one liquid during use, the isocyanate blocking agent is preferably used. It is preferable to use a phenol-based, alcohol-based, imine-based, oxime-based, lactam-based or active methylene-based compound having an isocyanate group blocked by reaction with an active hydrogen group-containing compound.

Examples of the monomer of the general formula (VI) or (VII) include the following. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, stearin Vinyl acid, monovinyl adipate, vinyl cyclohexanecarboxylate, vinyl salicylate, vinyl m-hydroxybenzoate, vinyl p-hydroxybenzoate, vinyl p-dimethylaminobenzoate, vinyl p-methylbenzoate, vinyl n-valerate, Vinyl isovalerate, vinyl D, L-2-methylbutyrate, vinyl monobromoacetate, vinyl 2,2-dimethylbutyrate, 2,
Vinyl 2-dimethylpentanoate, Vinyl 2-ethyl-2-methylbutyrate, Vinyl α-naphthenate, Vinyl β-Naphthenate, Vinyl monochloroacetate, Vinyl trifluoroacetate, Vinyl monochlorobenzoate, Vinyl persatic, Benzoic acid Vinyl, vinyl pt-butyl benzoate,
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, ethyl carbitol (meth) acrylate, (meth)
Propyl carbitol acrylate, butyl carbitol (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2
-Hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth)
Acrylate, glycerin mono (meth) acrylate,
Pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyl) Oxy) ethyl (meth) acrylate, glycidyl (meth) acrylate, 2,3-epoxypropyl (meth) acrylate, trimethoxyvinylsilane, triethoxyvinylsilane, dichloromethylvinylsilane, dimethylchlorovinylsilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, Diacetoxymethylvinylsilane, triacetoxyvinylsilane, triisopropoxyvinylsilane, trichlorovinylsilane, trime Ruvinylsilane, triethylvinylsilane, tri-t-butoxyvinylsilane, tri (ethoxymethoxy) vinylsilane, ethoxydiethylvinylsilane, methyl (vinyldimethylsilyl) acetate, diethylmethylvinylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyl Triethoxysilane, 3-methacryloyloxypropyltriisopropoxysilane, 3-methacryloyloxypropyldiacetoxymethylsilane, 3-methacryloyloxypropyltriacetoxysilane, 3
-Methacryloyloxypropyldiethoxymethylsilane, 3-methacryloyloxypropyltrimethylsilane, 3-methacryloyloxypropyltri-t-butoxysilane, 3-methacryloyloxypropylethoxydiethylsilane, 3-methacryloyloxypropyldiethylmethylsilane, 3-acryloyl Oxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltriisopropoxysilane, 3-acryloyloxypropyldiacetoxymethylsilane, 3-acryloyloxypropyldiethoxymethylsilane, 3-acryloyloxypropyl Triacetoxysilane, 3-acryloyloxypropyltrimethylsilane, 3-acryloyloxypropyl Tri -t- butoxysilane, 3-acryloyloxy propyl ethoxy diethyl silane, 3
-Acryloyloxypropyldiethylmethylsilane,
N- (3-methacryloyloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, methacryloyloxymethyldimethylethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltrimethylsilane, O -Methacryloyloxy (polyethyleneoxy) trimethylsilane, 3-
Methacryloyloxypropyldimethylchlorosilane,
3-methacryloyloxypropyldimethyl ethoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropylmethyldichlorosilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxy Propyltrichlorosilane, 3-methacryloyloxypropyltris (methoxyethoxy) silane, (2-
(Acryloyloxyethoxy) trimethylsilane, N-
3- (acryloyloxy-2-hydroxypropyl)
-3-aminopropyltriethoxysilane, 3-acryloyloxypropyldimethylmethoxysilane, 3-acryloyloxypropylmethyldichlorosilane, 3-
Acryloyloxypropylmethyldimethoxysilane,
3-acryloyloxypropyltrichlorosilane, acryloyloxytrimethylsilane, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, vinyl bromide, N-vinylcaprolactam,
N-vinylcarbazole, 4-vinylpyridine hydrochloride,
2-vinylpyridine hydrochloride, 1-vinyl-2-pyrrolidone, N-vinylpiperidone, 5-ethyl-2-vinylpyridine hydrochloride, 2-methyl-5-vinylpyridine hydrochloride, 2-isopropenylpyridine hydrochloride, allyl Alcohol and its ethylene oxide and / or propylene oxide adduct, allylamine hydrochloride, glycerin monoallyl ether, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, aminopropyl (Meth) acrylate, phenylaminoethyl methacrylate, cyclohexylaminomethyl methacrylate, N-vinylethylamine, N-acetylvinylamine, acrylamine, 2-acryloyloxyethyltrimethylammonium Chloride, 2-hydroxy-3-
Methacryloyloxypropyltrimethylammonium chloride, N-acryloyl tris (hydroxymethyl) aminomethane, (meth) acryloylmorpholine,
Acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N,
N-diethyl (meth) acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, N, N-dimethylaminopropyl (meth) acrylamide, N-2-hydroxyethyl (meth) acrylamide, N-2-hydroxypropyl (meth) ) Acrylamide, p-hydroxyphenyl (meth) acrylamide, α-methylol (meth) acrylamide, tri-n-butyl (2-methacryloyloxyethyl) phosphonium chloride, trioctyl (4-vinyl) phosphonium chloride, 2-
(Meth) acryloylethyl phosphoric acid, N, N, N ',
N'-tetrakis (β-hydroxyethyl) ethylenediamine acrylate, isocyanateethyl (meth) acrylate, isocyanatepropyl (meth) acrylate, isocyanatebutyl (meth) acrylate, isocyanatepentyl (meth) acrylate, isocyanatehexyl (meth) acrylate, 1- Methyl-2
-Isocyanatoethyl (meth) acrylate, 1,1
-Dimethyl-2-isocyanatoethyl (meth) acrylate, blocked adducts of these isocyanate alkyl (meth) acrylates, and reaction products of an active hydrogen group-containing vinyl monomer with a polyfunctional isocyanate compound.

Examples of the blocked isocyanate alkyl (meth) acrylate adduct include isocyanate ethyl methacrylate butyl urethane, isocyanate ethyl methacrylate octyl urethane, isocyanate ethyl methacrylate-caprolactam adduct, isocyanate ethyl methacrylate-butyrolactam adduct, and isocyanate ethyl methacrylate -Methyl ethyl ketoxime adduct (trade name, manufactured by Showa Denko KK, "Karenz MOI-BM") and the like.

In the above reaction product of the active hydrogen group-containing vinyl monomer and the polyfunctional isocyanate compound,
The vinyl monomer having an active hydrogen group used as a raw material is preferably a vinyl monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-
3-phenoxypropyl (meth) acrylate, hydroxyethylcellulose (meth) acrylate, N-2-
Hydroxyethyl (meth) acrylamide, N-2-hydroxypropyl (meth) acrylamide, p-hydroxyphenyl (meth) acrylamide and the like are used.
In addition, amino group-containing vinyl monomers and mercapto group-containing vinyl monomers can also be used.

The polyfunctional isocyanate compound also used as a raw material includes, for example, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3 '-Dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, m-xylylene diisocyanate, tetramethyl xylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, trans-1,4-cyclohexylene diisocyanate, lysine diisocyanate, Methyl cyclohexane diisocyanate, diisocyanate methyl cyclohexane, dimer acid diisocyanate, isopropyl Denbisu (4-cyclohexyl isocyanate), diphenylmethane diisocyanate,
Examples include diisocyanate compounds such as tolylene diisocyanate, monomers composed of compounds having three or more isocyanate groups such as triphenylmethane triisocyanate, lysine triisocyanate, and dimethyltriphenylmethane tetraisocyanate, and polymers thereof. Also, these various modified products and adducts, such as urethane modified products, allophanate modified products, biuret modified products, carbodiimide modified products, uretonimine modified products,
Examples include uretdione-modified products, isocyanurate-modified products, acylurea-modified products, and trimethylolpropane adducts. These raw materials may be used alone, or 2
A combination of more than one species may be used. Examples of the reaction product of the active hydrogen group-containing vinyl monomer and the polyfunctional isocyanate compound include, for example, a reaction product of a hydroxyl group-containing vinyl monomer and a diisocyanate compound. And urethane bond-containing compounds.

In the process for preparing the compound of the general formula (II), in particular, the compound P, the peroxide (I), ie, perfluorodecalin carbonyl peroxide, and a monomer having an ethylenic polymerizable group, in particular, a monomer of the general formula (VI) ( When the monomer (A) and / or the monomer of the formula (VII) (hereinafter also referred to as monomer B) is reacted, the monomer is entirely in a molar ratio of 0.1 to 5000 with respect to the peroxide (I). , Especially 0.5 to 1000
It is preferable to set it in the range. If the ratio is less than 0.1, a large amount of products resulting from the self-decomposition of the peroxide (I) are generated, and if it exceeds 5,000, the yield of the target compound is undesirably reduced. Monomer A and Monomer B
When (at least two, preferably two) monomers are used, the proportion of each monomer used can be arbitrarily determined. However, when only monomer B has a reactive group such as an isocyanate group or a trialkoxysilyl group, A range where the molar ratio of the monomer A to the monomer B does not exceed 100,
Among them, it is preferable to set the range not to exceed 20. When the ratio exceeds 100, the ratio of the active group introduced into the compound becomes small, and the bonding force and the adsorptivity to the substrate, especially to the surface thereof, decrease.

Further, by adjusting the molar ratio of the monomer to the peroxide, the molecular weight of the obtained product is about 900 to 1,000,000, preferably about 950 to 1,000,000.
It can be adjusted to 100,000. That is, for example, if this ratio is reduced and the peroxide is higher than the monomer with respect to the charged molar amount, a low-molecular-weight target compound can be obtained. If the product is lower than the monomer, a high molecular weight target compound can be obtained.

The reaction conditions in the above method vary depending on the types of various raw materials, the proportions used, and the like.
Normal pressure is used as the pressure, the reaction temperature is -20 to 150 ° C,
Preferably, a range of 0 to 100 ° C is used. If the reaction temperature is lower than −20 ° C., the reaction time becomes longer.
If the temperature exceeds 50 ° C., the pressure during the reaction becomes too high, and it becomes difficult to control the reaction system (reaction operation). The reaction time is usually selected in the range of 0.5 to 20 hours, but it is desirable to set conditions so that it is practically 1 to 10 hours.

By reacting perfluorodecalin carbonyl peroxide with the above-mentioned monomer in this way, the desired perfluorodecalyl group-containing compound can be directly obtained in a one-step reaction. It is preferable to use a solvent.

As such organic solvents, halogenated aliphatic solvents and halogenated aromatic solvents are particularly preferred. Specifically, for example, methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2
-Dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-
2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, 1,1,1 , 2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3
-Pentafluoro-1,3-dichloropropane, benzotrifluoride, hexafluoroxylene, pentafluorobenzene and the like. Particularly, industrially, 1,1,2-trichlorotrifluoroethane, 1,1,1
1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride, or a mixture of these in any proportion Solvent [for example, AK-225 (1,1,1,2,2-pentafluoro-3,3-dichloropropane and 1,1,2,2,3-
A mixed solvent with pentafluoro-1,3-dichloropropane)]. When the solvent is used, the concentration of perfluorodecalin carbonyl peroxide in the solvent is usually 0.1 to 50% by weight, preferably 0.1 to 30% by weight.

The general formula (I) obtained by the above method
Compounds of I), especially compound P, can be obtained by distillation, recrystallization,
It can be purified by a known method such as a reprecipitation method, a column chromatography method, and a dialysis method.

In addition, the peroxide (I) of the present invention can be reacted with various reactive compounds, especially an aromatic compound, in addition to the above reaction to introduce a perfluorodecalyl group. Among the thus obtained compounds, the compounds represented by the general formula (II)
With respect to the perfluorodecalyl group-containing compound represented by I), the aromatic residue is not particularly limited as long as it is a residue of an aromatic compound having no polymerizability. Preferred examples thereof include benzene, toluene, and xylene. , Ethylbenzene, biphenyl, bibenzyl, naphthalene, indene, phenanthrene, thiophene, furan, pyrrole,
Residues of lutidine or benzofuran, among others, benzene, thiophene, furan, toluene, xylene or naphthalene.

In the perfluorodecalyl group-containing compound represented by the general formula (IV), the aromatic residue is not particularly limited as long as it is a polymerizable aromatic compound or a residue of a polymer thereof. Preferable ones include, for example, polystyrene residues having a molecular weight of 200 to 2,000,000.

In the preparation of these perfluorodecalyl group-containing compounds, the molar ratio of the aromatic compound to perfluorodecalin carbonyl peroxide can be set to an arbitrary ratio, but is preferably 1: 0.01 to 1: 0.01. 100, especially 1: 0.5
It is preferably in the range of from 50 to 50 (in the case of polystyrene, the molar ratio in terms of monomer is used). If the charged molar ratio of the aromatic compound as the raw material is less than 0.01, a large amount of a product resulting from the self-decomposition of peroxide is generated, and if it exceeds 100, a large amount of unreacted material remains, which is not preferable. .

The reaction can be carried out at normal pressure,
The reaction temperature is −20 to 150 ° C., preferably 0 to 100 ° C.
It is desirable to be in the range of ° C. The reaction temperature is -20
If the temperature is lower than 150 ° C., the reaction time is prolonged. If the temperature exceeds 150 ° C., the pressure during the reaction becomes too high, which makes it difficult to control the reaction system (reaction operation). The reaction time is usually selected in the range of 0.5 to 20 hours, but it is desirable to set conditions so that it is practically 1 to 10 hours.

In this way, by reacting perfluorodecalin carbonyl peroxide with the aromatic compound, the desired perfluorodecalyl group-containing compound can be directly obtained in a one-step reaction. It is preferable to use an organic solvent.

As such organic solvents, halogenated aliphatic solvents and halogenated aromatic solvents are particularly preferred. Specifically, for example, methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2
-Dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-
2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, 1,1,1 , 2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3
-Pentafluoro-1,3-dichloropropane, benzotrifluoride, hexafluoroxylene, pentafluorobenzene and the like. Particularly, industrially, 1,1,2-trichlorotrifluoroethane, 1,1,1
1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, benzotrifluoride, or a mixture of these in any proportion Solvent [for example, AK-225 (1,1,1,2,2-pentafluoro-3,3-dichloropropane and 1,1,2,2,3-
A mixed solvent with pentafluoro-1,3-dichloropropane)]. When the solvent is used, the concentration of perfluorodecalin carbonyl peroxide in the solvent is usually 0.1 to 50% by weight, preferably 0.1 to 30% by weight.

The thus obtained general formula (II)
The perfluorodecalyl group-containing compound represented by I) and the general formula (IV) can be purified by a known method such as a distillation method, a recrystallization method, a reprecipitation method, a column chromatography method, and a dialysis method.

Further, as the compound of the general formula (IV),

Embedded image (Wherein, Rf is a 1-perfluorodecalyl group and / or 2-perfluorodecalyl group, x is an integer of 0 to 10000, and y is an integer of 1 to 10000). This compound is obtained by converting styrene into a perfluorodecalyl group represented by the general formula: RfC (＝ O) OO (O ＝) CRf (wherein Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group) It can be produced by reacting with a contained peroxide.

[0042]

The perfluorodecalin carbonyl peroxide of the present invention is a novel compound, which is used as a polymerization initiator for a monomer having an ethylenic polymerizable group, and as a perfluorodecalyl group-introducing agent by itself, In other words, it is useful as a perfluorodecalylating agent. The various perfluorodecalyl group-containing compounds of the present invention are also novel compounds, and the perfluorodecalyl group is directly bonded by a carbon-carbon bond instead of a bond such as an ester bond, which is slightly difficult for long-term stability. For,
Long-lasting properties due to fluorine, low surface tension and low refractive index, weather resistance, heat resistance, cold resistance, oil resistance, electrical insulation, anti-fogging, anti-fouling, chemical resistance Excellent, etc., therefore, it is useful as a new fluorine-based surfactant, and furthermore, a surface treatment agent, a paint, an optical lens,
It is used as a surface material for plastic optical fibers, eyeglass lenses, glassware, and the like, and as a raw material for cosmetics. Further, according to the production method of the present invention, various perfluorodecalyl group-containing compounds can be obtained easily and in a short time with a high yield in a one-step reaction without using a reaction catalyst or a special device.

[0043]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. As for the means for analyzing the compounds, FT-IR8200PC manufactured by Shimadzu Corporation was used for the IR spectrum analysis, and Unity manufactured by Varian was used for the NMR spectrum.
plus500 (500 MHz) was used. The molecular weight was measured using a high-performance liquid chromatography LC-6AD manufactured by Shimadzu Corporation (differential refractive index detector: RID-6A, column: GPC KF-802.5 manufactured by SHOdex) according to a calibration curve of standard pullulan. Was measured for molecular weight. The surface tension was measured using a surface tension meter CBVP-A3 manufactured by Kyowa Interface Science. In Examples 3-8 ¹ for polymer A~F obtained by H-NMR chloroform -d ₁ as a solvent for measurement (deuterated chloroform) (Kanto Chemical, for NMR, Compound A, B, C, E, use to F) or dimethyl sulfoxide -d ₆ (manufactured by Kanto Chemical Co., N
(For MR, used for compound D). In addition, FT-
The measurement unit of IR is cm ⁻¹ , and the measurement unit (δ) of NMR is p
pm.

Synthesis Example 1 In a 200 ml reactor equipped with a distillation apparatus, 48.9 g of α-perfluorodecalin carboxylic acid, 11.1 g of phosphoryl trichloride and 3.70 g of dimethylformamide were charged, and heated at 70 ° C. for 20 minutes. After the reaction, the reaction was terminated by cooling. Subsequently, the obtained reaction liquid was distilled under reduced pressure while heating again, and the reaction liquid was 87 to 90 ° C./15 mmHg.
, A main fraction was obtained, dried over magnesium sulfate, and subjected to suction filtration to obtain 22.8 g of α-perfluorodecalin carboxylic acid chloride (yield: 45%). The IR absorption spectrum of the, due to -OH group of the starting material disappeared, also due to the -C = O groups had shifted to 1805cm ^-1 from 1786 cm ^-1 in the raw material.

Synthesis Example 2 48.9 g of α-perfluorodecalin carboxylic acid was added to β-
Same as Synthesis Example 1 except that 4.89 g of perfluorodecalin carboxylic acid, the doses of phosphoryl trichloride and dimethylformamide were 1.2 g and 0.4 g, respectively, and the reaction conditions were changed to heating at 80 ° C. for 150 minutes. React
Separation treatment provided 1.45 g (yield 28%) of β-perfluorodecalin carboxylic acid chloride. IR of this thing
The absorption spectra, due to the -OH group of the starting material disappeared, also due to the -C = O groups had shifted to 1803cm ^-1 from 1786 cm ^-1 in the raw material.

Example 1 0.72 g of sodium hydroxide and 6.52 g of water were placed in a 300 ml reactor equipped with a stirrer, a cooler and a temperature controller.
Was added and dissolved sufficiently, and AK-225 was added thereto.
(1,1,1,2,2-pentafluoro- manufactured by Asahi Glass Co., Ltd.
Mixed solvent of 3,3-dichloropropane and 1,1,2,2,3-pentafluoro-1,3-dichloropropane) 1
00 g was added. The reactor was cooled to −5 ° C. in an ice bath to which sodium chloride had been added, and 2.04 g of hydrogen peroxide cooled to −5 ° C. was added thereto, and then α-perfluorodecalin carboxylic acid obtained in Synthesis Example 1 was added. Acid chloride 5.0
1 g was completely dissolved in 5.00 g of AK-225 solvent,
After the solution cooled to 5 ° C was added dropwise at -9 to -3 ° C over 7 minutes, the mixture was reacted at -5 to 0 ° C for 30 minutes. The reaction solution was washed with 300 ml of cold water, the water was changed, and the same washing operation was repeated several times to sufficiently wash the solution.

Embedded image 2.19 g (yield 45%) of bis (perfluorodecalin-1-carbonyl) peroxide (hereinafter referred to as peroxide X) of a perfluoro organic peroxide represented by the following formula:
In the IR absorption spectrum, those attributable to the -C = O group were detected at 1865 cm ^-1 and 1827 cm ^-1 . The thermal decomposition rate of this product was measured as follows. That is, this is thermally decomposed in a reaction tube sufficiently purged with nitrogen at a constant temperature for a predetermined time, and then added to a mixed solution of 1 ml of a saturated potassium iodide aqueous solution, 10 ml of isopropyl alcohol and 1 ml of acetic acid for 3 minutes. After heating, titration was performed with a 0.01 N sodium thiosulfate standard solution, and the remaining amount of peroxide was measured. Table 1 shows the results.

[0047]

[Table 1]

From the results, it was found that the peroxide of the present invention has a selected half-life temperature of 8.2 ° C. for 10 hours, and enables efficient α-perfluorodecalyl group introduction even under mild conditions.

Example 2 The procedure of Example 1 was repeated, except that 5.01 g of α-perfluorodecalin carboxylic acid chloride obtained in Synthesis Example 1 was replaced with 5.01 g of β-perfluorodecalin carboxylic acid chloride obtained in Synthesis Example 2. React, separate and treat

Embedded image 1.95 bis (perfluorodecalin-2-carbonyl) peroxide (hereinafter referred to as peroxide Y)
g (40% yield). In the IR absorption spectrum, those attributable to the -C = O group were detected at 1860 cm ^-1 and 1825 cm ^-1 .

Example 3 0.77 g of acrylic acid was added to a 300 ml reactor equipped with a stirrer, a cooler and a temperature controller.
1.04 g of the peroxide X obtained in
Then, a solution dissolved in 00 g was added thereto, and the mixture was cooled to
Allowed to react for hours. The obtained reaction solution is subjected to suction filtration, vacuum-dried, and

Embedded image 0.93 g (yield 54%) of a slightly yellow perfluorodecalyl group-containing polymer represented by the following formula:
I got The number average molecular weight of this product was 6040 when determined by gel filtration using tetrahydrofuran as a solvent.
(2.95). The spectrum data of this is shown below. FT-IR; 3250 (OH), 1726
(C = O), 1243 ( CF 2) 1 H-NMR; 1.40
_{~2.10 (CH 2), 2.10~2.82 (} CH)

Example 4 The procedure of Example 3 was repeated, except that peroxide X was replaced with peroxide Y.

Embedded image 0.26 g (yield 15%) of a slightly yellow perfluorodecalyl group-containing polymer represented by the following formula (hereinafter, referred to as compound B):
I got The number average molecular weight of this compound was 4560 when determined by gel filtration using tetrahydrofuran as a solvent.
(3.11). The spectrum data of this is shown below. FT-IR; 3245 (OH), 1720 (C = O),
^{_{1238 (CF 2) 1 H-}} NMR; 1.38~2.15 (CH 2), 2.16
~ 2.88 (CH)

Example 5 0.77 g of acrylic acid was added to diacetone acrylamide [N
-(1,1-dimethyl-3-oxobutyl) acrylamide] 1.40 g, the amount of peroxide X charged was 0.81 g
The reaction was carried out in the same manner as in Example 3 except that the reaction was changed to. The obtained compound is reprecipitated in a methanol-water system, filtered by suction, dried in vacuo,

Embedded image 1.93 g (yield 90%) of a pale yellow perfluorodecalyl group-containing polymer represented by the following formula:
I got The number average molecular weight of this compound was found to be 3710 by gel filtration using tetrahydrofuran as a solvent.
(2.33). The spectrum data of this is shown below. FT-IR; 3369 (NH), 1711, 1653
(C = O), 1252 ( CF 2) 1 H-NMR; 1.00~2.03 (CH 2), 1.34
_{(CH 3), 2.03~2.78 (CH} 2, CH)

Example 6 0.77 g of acrylic acid was added to 3-methacryloxy-2-hydroxypropyltrimethylammonium chloride 1.1
The reaction was carried out in the same manner as in Example 2 except that the amount of peroxide X was changed to 0.30 g to 0 g. The obtained compound is reprecipitated in a methanol-acetone system, and subjected to suction filtration.
Vacuum dry and formula

Embedded image 0.64 g (yield 47%) of a pale yellow perfluorodecalyl group-containing polymer represented by the following formula (hereinafter referred to as compound D):
I got The number average molecular weight of this compound was 4950 (1.9) as determined by gel filtration using methanol as a solvent.
5). The spectrum data of this is shown below. FT-IR (cm ^-1 ); 3388 (OH), 1712
(C = O), 1249,1217 ( CF 2) 1 H-NMR; 0.60~2.00 (CH 3, CH 2,
CH), 2.82 to 3.31 (N ⁺ CH ₃ ), 4.14 to
4.60 (CH ₂ )

Example 7 0.77 g of acrylic acid was added to dimethylacrylamide 1.0
The reaction was carried out in the same manner as in Example 2 except that the amount of peroxide X was changed to 1.04 g to 6 g. The obtained compound is reprecipitated in a methanol-water system, filtered by suction, dried in vacuo,

Embedded imageA pale yellow perfluorodecalyl group-containing polymerization represented by
1.73 g of a compound (hereinafter, referred to as compound E) (86% yield)
I got The number average molecular weight of this product is
When determined by gel filtration method using lofran, 1230
(2.12). This spectral data is
It is shown below. FT-IR (cm^-13430 [C (= O) NMe
_Two], 1643 (C = O), 1211 (CF_Two)¹ H-NMR; 1.04 to 2.00 (CH_Two), 2.2
6 to 3.36 (CH _Three, CH)

Example 8 An isocyanate ethyl methacrylate-methyl ethyl ketone oxime adduct (trade name, manufactured by Showa Denko KK) was placed in a 300 ml reactor equipped with a stirrer, a cooler, and a temperature controller.
7.26 g of "Karenz MO1-BM") and dimethylacrylamide (trade name, manufactured by Kojin Co., Ltd., "DMAA")
97 g of the mixture was charged, and 9.74 g of peroxide X was AK
A solution dissolved in -225 solvent (100 g) was added, and the mixture was reacted at 45 ° C for 5 hours under a nitrogen stream. The compound thus obtained was reprecipitated in a methanol-hexane system, filtered by suction, dried in vacuo, and treated with the formula

Embedded image 12.98 g (yield: 68%) of a perfluorodecalyl group-containing polymer represented by the following formula (hereinafter, referred to as compound F) was obtained. The number average molecular weight of this compound was determined to be 4110 (2.
87). The spectrum data of this is shown below. FT-IR; 1658 (C = O), 1726 (-N = C
−), 3350 (NH), 1235 (CF ₂ ) ¹ H-NMR; 4.12, 3.52 (CH ₂ ), 0.80
３3.21 (CH ₂ , CH ₃ ) Further, as a result of calculating the copolymerization ratio by ¹ H-NMR using the above apparatus using deuterated chloroform as a solvent, x: y = 5
3:47.

From the results of Examples 3 to 8, it is found that bis (perfluorodecalincarbonyl) peroxide of the peroxide of the present invention is useful as a radical polymerization initiator for a compound having a polymerizable group having ethylene.

With respect to the compounds obtained in Examples 3 to 8,
The solubility in various solvents was examined and evaluated according to the following criteria.
Table 3 shows the results. ：: dissolves. Δ: Although dissolved, it becomes cloudy. ×: Does not dissolve.

[0058]

[Table 2]

From Table 2, it was found that these polymers were soluble in a wide range of solvents.

(2) Surface tension characteristics The polymer A obtained in Example 3 was dissolved in water at various concentrations as shown in the following table, and the surface tension at 25 ° C. was measured by the Wilhelmy method using the above apparatus. did. Table 3 shows the results.

[Table 3] Table 3 shows that the compound of the present invention efficiently reduces the surface tension of water.

Example 9 A 300 ml reactor equipped with a stirrer, a cooler and a temperature controller was charged with 0.78 g of benzene, and a peroxide X1 was added.
A solution obtained by dissolving 9.48 g in 100 g of AK-225 solvent was added, and the mixture was reacted at 45 ° C. for 8 hours under a nitrogen stream. The compound thus obtained was washed in the order of 300 ml of water, 300 ml of a 5% aqueous solution of sodium carbonate and 300 ml of water, dried over magnesium sulfate, and distilled under reduced pressure to obtain α.
1.82 g of perfluorodecalylbenzene (yield 35
%). The spectrum data of this is shown below. FT-IR; 742, 3000 (CH), 1235 (C
^{_{F 2) 1 H-NMR;}} 7.21~7.66 (C 6 H 5) The compounds are useful as novel fluorinated solvent.

Example 10 10 g of a solution obtained by dissolving 0.49 g of peroxide X in an AK-225 solvent was added to 10 g of a solution of polystyrene (0.5 g) (5 mmol as a styrene monomer unit) in methylene chloride. The reaction was carried out at 45 ° C. for 10 hours in an air stream. The obtained crude product is washed with water and a 5% aqueous solution of sodium carbonate, dried over magnesium sulfate, and then reprecipitated with a chloroform-methanol system to obtain a crude product.

Embedded image 0.40 g of polystyrene into which an α-perfluorodecalyl group represented by was introduced. The number average molecular weight of this product was 110000 (Mw / Mn = 2.21), and the rate of introduction of the perfluorodecalyl group determined from x and y in the above formula by the following formula [y / (x + y)] × 100 was 6 %
Met. In the FT-IR spectrum data after the introduction, a peak at 1278 cm ⁻¹ due to CF was detected. This indicates that the novel bis (perfluorodecalin-1-carbonyl) peroxide of the present invention is useful as an α-perfluorodecalyl group-introducing agent.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA01 AB40 AB81 EA35 EA36 EA37 EA43 4J015 BA06 4J100 AB02P AB07Q BB18Q CA04

Claims (17)

[Claims] 1. A perfluorodecalyl group-containing compound represented by the general formula: RfC (＝ O) OO (O）) CRf, wherein Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group. Peroxide. 2. The peroxide containing a perfluorodecalyl group according to claim 1, wherein Rf is a 1-perfluorodecalyl group. 3. A polymerization initiator for a monomer having an ethylenically polymerizable group, comprising the peroxide containing a perfluorodecalyl group according to claim 1 or 2 as an active ingredient. 4. A perfluorodecalyl group-introducing agent comprising the peroxide containing a perfluorodecalyl group according to claim 1 or 2. 5. A compound represented by the general formula: Rf- (A) m- (B) n-Rf wherein Rf is a 1-perfluorodecalyl group and / or 2-perfluorodecalyl group, and A and B are different ethylene groups. M and n are 0 to 1
To 5000 (where m + n ≠ 0) respectively]. 6. A compound of the general formula Rf- (CH_TwoCR¹R^Two) M- (CH_TwoCR^ThreeR^Four) N-R
f} wherein Rf is a 1-perfluorodecalyl group and / or
A 2-perfluorodecalyl group is represented by R¹And R^ThreeAre the same
Hydrogen atoms or alkyl groups which are or different from each other
And R^TwoAnd R^FourAre different from each other,
Group, 1-pyrrolidinyl group, halogen atom, cyano group,
-SiR^aR^a'R^a″ (Where R^a, R^a', R^a″ Is the same
One or different carbon atoms having 1 to 10 carbon atoms.
Alkyl group, alkoxy group or alkano having 1 to 4 carbon atoms
Represents an yloxy group, a halogen atom, or a hydrogen atom),
-CO_TwoR^FiveOr -CONR⁶R⁷[Where R^Five, R⁶, R
⁷Are the same or different from each other,
It may have a cycloalkyl group having a prime number of 1 to 18.
Alkyl group, cycloalkyl group, glycidyl group, -D-
Q (where D is a urethane bond, an ester bond, an amide
Bond, oxygen atom or nitrogen atom optionally intervening
Q is an isocyanate group (-NCO)
Or a blocked isocyanate group),-
(Y¹)_a− (Y ^Two-O)_b-R⁸[Where Y¹, Y^TwoAre the same
Or alkyls having 1 to 6 carbon atoms which are different from each other
Rene group is represented by R⁸Is a hydrogen atom, an alkyl group or -SiR^bR
^b'R^b″ (Where R^b, R^b', R^b″ Are the same
Or an alkyl group, an alkoxy group,
Represents a hydrogen atom, an alkanoyloxy group or a hydrogen atom
A) is 0 or 1, b is an integer of 0 to 20
Or hydroxyalkyl having 1 to 20 carbon atoms
Group, aminoalkyl group, alkylaminoalkyl group or
Dialkylaminoalkyl groups or their ammonium
Salt, cyanoalkyl group, alkylthioalkyl group,
Kilphosphonium group, phosphoalkyl group, or glycidyl
And R represents an alkyl group.⁶And R⁷Are each other
To form a heterocycle with N to which they are attached
May be used], -OCOR^Five(Where R^FiveIs the same as above
Taste) or -Y¹-(O-Y^Two)_b-R⁹(here
And Y¹, Y^TwoAre the same or different, charcoal
R 1 represents an alkylene group having a prime number of 1 to 6⁹Is hydroxyl or alcohol
A xy group, b represents an integer of 0 to 20),
m and n are each 0 to 5000 (however, m + n ≠ 0)
Perfluorodecalyl group-containing compound represented by｝
object. 7. A compound of the general formula: Ar-Rf (wherein, Ar is a non-polymerizable aromatic compound residue, Rf is a 1-perfluorodecalyl group and / or 2-
Which is bonded to a carbon atom of an aromatic ring by a perfluorodecalyl group). 8. The residue of the non-polymerizable aromatic compound is a residue of benzene, toluene, xylene, ethylbenzene, biphenyl, bibenzyl, naphthalene, indene, phenanthrene, thiophene, furan, pyrrole, lutidine or benzofuran. 8. The perfluorodecalyl group-containing compound according to 7. 9. A compound of the general formula (Ar'-H) x (Ar'-Rf) y, wherein Ar 'is a polymerizable aromatic monomer unit residue, and Rf is a 1-perfluorodecalyl group and / Or a 2-perfluorodecalyl group bonded to a carbon atom of an aromatic ring, x is an integer of 0 to 10000, and y is 1 to 10000
A perfluorodecalyl group-containing compound represented by the formula: 10. A compound of the general formula (Wherein, Rf is a 1-perfluorodecalyl group and / or 2-perfluorodecalyl group, x is an integer of 0 to 10000, and y is an integer of 1 to 10000). 11. A perfluorodecalin carboxylic acid halide represented by the general formula RfC (＝ O) X (wherein, Rf is a 1-perfluorodecalyl group and / or 2-perfluorodecalyl group, and X is a halogen atom). Is reacted with at least one member selected from the group consisting of hydrogen peroxide, sodium peroxide, potassium peroxide and barium peroxide, the perfluorodecalyl group-containing peroxide according to claim 1 or 2, wherein Method. 12. A monomer having one or more ethylenic polymerizable groups represented by the general formula: RfC (＝ O) OO (O ＝) CRf (where Rf is a 1-perfluorodecalyl group and / or 2- 6. The method for producing a perfluorodecalyl group-containing compound according to claim 5, wherein the compound is reacted with a perfluorodecalyl group-containing peroxide represented by the following formula: 13. The general formula CH_Two= CR¹R^Two And CH_Two= CR^ThreeR^Four 中 where R¹And R^ThreeAre the same or different
A hydrogen atom or an alkyl group^TwoAnd R^FourAre different from each other
A piperidino group, 1-pyrrolidinyl
Group, halogen atom, cyano group, -SiR^aR^a'R^a″
(Where R^a, R^a', R^a″ Is the same or
C1-C10 alkyl groups different from each other, C1
To 4, an alkoxy group or an alkanoyloxy group, a halo
Gen atom or hydrogen atom), -CO_TwoR^FiveOr -C
ONR⁶R⁷[Where R^Five, R⁶, R⁷Are the same
Or a hydrogen atom, a C1-18
An alkyl group optionally having a cycloalkyl group,
Alkyl group, glycidyl group, -DQ (where D is
Rethane bond, ester bond, amide bond, oxygen atom or
A divalent saturated hydrocarbon group optionally interposed by a nitrogen atom,
Q is an isocyanate group (-NCO) or
Each represents a cyanate group),-(Y¹)_a− (Y ^Two−
O)_b-R⁸[Where Y¹, Y^TwoAre the same or
A different alkylene group having 1 to 6 carbon atoms is represented by R⁸Is
Hydrogen atom, alkyl group or -SiR^bR^b'R^b"(here
And R^b, R^b', R^b″ Are the same or
Different, alkyl, alkoxy, halogen,
A represents a lucanoyloxy group or a hydrogen atom), a is 0 or
1, b represents an integer of 0 to 20], or carbon
Hydroxyalkyl group, aminoalkyl of formulas 1 to 20
Group, alkylaminoalkyl group or dialkylamino group
Alkyl group or their ammonium salts, cyanoalkyl
Group, alkylthioalkyl group, alkylphosphonium
Group, a phosphoalkyl group, or a glycidylalkyl group.
And R⁶And R⁷Are connected to each other
May form a heterocyclic ring with the N to which they are bonded.]
COR^Five(Where R^FiveHas the same meaning as above)
Is -Y¹-(O-Y^Two)_b-R⁹(Where Y¹, Y^TwoAre the same
Or alkyls having 1 to 6 carbon atoms which are different from each other
Rene group is represented by R⁹Represents a hydroxyl group or an alkoxy group, and b represents 0 to
20 represents an integer of 20).
And at least one selected from the monomers represented by the general formula: RfC (= O) OO (O =) CRf (where Rf is a 1-perfluorodecalyl group and / or
Represents a 2-perfluorodecalyl group)
It is characterized by reacting with a fluorodecalyl group-containing peroxide.
7. A perfluorodecalyl group-containing compound according to claim 6, wherein
Manufacturing method of compound. 14. An aromatic compound represented by the general formula Ar-H (wherein, Ar is a non-polymerizable aromatic compound residue, and a bond of which is located on an aromatic ring) is represented by the general formula RfC Reacting with a perfluorodecalyl group-containing peroxide represented by (= O) OO (O =) CRf (wherein Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group). The method for producing a perfluorodecalyl group-containing compound according to claim 7, characterized in that: 15. The aromatic compound is benzene, toluene,
Xylene, ethylbenzene, biphenyl, bibenzyl,
Naphthalene, indene, phenanthrene, thiophene,
The method according to claim 14, which is furan, pyrrole, lutidine, or benzofuran. 16. A polymerizable aromatic compound represented by the general formula: Ar ″ —H (wherein, Ar ″ is a polymerizable aromatic monomer residue, and a bond thereof is located on an aromatic ring). The monomer is represented by the general formula RfC (= O)
Reacting with a perfluorodecalyl group-containing peroxide represented by OO (O =) CRf (wherein, Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group). Item 10. The method for producing a perfluorodecalyl group-containing compound according to Item 9. 17. Perfluorodecalyl represented by the general formula RfC (＝ O) OO (O ＝) CRf, wherein Rf represents a 1-perfluorodecalyl group and / or a 2-perfluorodecalyl group. The method for producing a perfluorodecalyl group-containing compound according to claim 10, wherein the compound is reacted with a group-containing peroxide.