JPH1060027A - New fluorine-containing macroazo compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having in the molecule segments each bearing many fluorine atoms, and capable of efficiently incorporating many fluorine atoms into a polymer by carrying out a polymerization as a macroazo initiator. SOLUTION: This new compound is composed of recurring unit of formula I (R<1> and R<3> are each a lower alkyl; R<2> and R<4> are each a lower alkyl or cyano; A1 , and A2 are each O or a lower alkylene; Z1 , and Z2 are each ester linkage or amido linkage; T1 and T2 are each CONH or a lone pair; Q is a fluorine- contg. segment). The polymerization degree of this compound is pref. 2-100. This compound is obtained, pref., for example, by reaction of an azo compound of formula II with a fluorine-contg. ether compound of formula III in an appropriate solvent, in the presence of a basic catalyst if needed, and also in an inert gas atmosphere if needed, by the use of a dehydrating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fluorine-containing azo compound having a fluorine segment in a molecule, which is useful, for example, as a polymerization initiator.

[0002]

2. Description of the Related Art In recent years, as the fields of application of polymer materials have been diversified, polymers having various physical properties have been required. In particular, a polymer having a perfluoroalkylene group (Rf group) in the molecule has a low surface free energy of the Rf group, so the Rf group portion is concentrated on the polymer surface, and excellent water repellency, oil repellency, heat resistance, It has attracted attention because it exhibits weather resistance, slip characteristics, and the like.

Heretofore, attempts have been made to introduce a polymer having an Rf group into a base by a method such as blending, but a sufficient effect has not yet been obtained. Therefore, various attempts to introduce an Rf group into a polymer have been studied. For example, a method of introducing an Rf group by reacting a polymer obtained by living anionic polymerization with an alkyl halide having an Rf group has been reported (Po.
lymer Preprints Japan., 44 948 (1995). Also,
There is also known a method of producing a polymer having a fluorine segment by performing a polymerization reaction using a fluorine-containing monomer. Among them, particularly, a method for synthesizing a block polymer using a monomer having a perfluoroalkylene group has been energetically studied because a perfluoroalkylene group can be efficiently introduced into a molecule at a high concentration. However, in the method of reacting a polymer with an alkyl halide having an Rf group, usable polymers are limited, and thus have disadvantages such as poor reactivity. Further, in the method of performing a polymerization reaction using a fluorine-containing monomer, it is difficult to introduce a fluorine segment at a target position in a polymer, and there is a problem that a block polymer is not obtained. .

[0004] As means for solving such problems,
Attempts have been made to introduce a fluorine segment by subjecting a prepolymer having a fluorine-containing alkylene group to a condensation reaction with a polymer. However, since the solubility of the prepolymer having a fluorine-containing alkylene group is poor, it has been difficult to introduce a fluorine segment with a high yield.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is intended to provide a fluorine-containing macroazo compound useful for efficiently introducing a fluorine segment into a polymer and a fluorine-containing macroazo compound derived therefrom. An object is to provide a block polymer having a fluorine unit in a molecule.

[0006]

The present invention provides a compound represented by the general formula [1]:

[0007]

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(Wherein R ¹ and R ³ each independently represent a lower alkyl group, R ² and R ⁴ each independently represent a lower alkyl group or a cyano group, and A ₁ and A ₂ represent Each independently represents an oxygen atom and / or a lower alkylene group which may be via an aromatic ring, Z ₁ and Z ₂ each independently represent an ester bond or an amide bond, and T ₁ and T ₂ each represent Independently represents -CONH- or a bond, and Q represents a fluorine-containing segment.)

Further, the present invention is an invention of a method for polymerizing a monomer, characterized by using the above-mentioned fluorine-containing macroazo compound.

[0010] The present invention is also a macroazo initiator comprising the above-mentioned fluorine-containing macroazo compound.

Further, the present invention is an invention of a fluorine-containing block polymer obtained by polymerizing a monomer using the above-mentioned fluorine-containing macroazo compound.

Further, the present invention is an invention of a fluorine-containing block polymer comprising, as constituents, a unit derived from the above-mentioned fluorine-containing macroazo compound and a monomer unit.

In the general formula [1], the lower alkyl group represented by R ^{1 to} R ⁴ may be linear or branched and includes, for example, an alkyl group having 1 to 6 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group,
sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1-methylpentyl group, n-
Examples include a hexyl group and an isohexyl group. The lower alkylene group which may be via an oxygen atom and / or an aromatic ring represented by A ₁ and A ₂ may be linear or branched, and includes, for example, an alkylene group having 1 to 6 carbon atoms. When an oxygen atom may be interposed, one or more, preferably 1 to 5, more preferably 1 to 3, -O- groups are provided at the terminal of the alkylene group or at an arbitrary position in the chain.
In the case where an aromatic ring may be interposed, an aromatic ring such as a phenylene group or a diphenylene group may be provided at the terminal of the alkylene group or at an arbitrary position in the chain. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, and 2-
Methyl propylene group, pentylene group, 2,2-dimethyl propylene group, 2-ethyl propylene group, hexylene group, -CH ₂
-C ₆ H ₄ -group, o-xylene-α, α'-diyl group, -O-CH ₂ -group,-
O-CH ₂ CH ₂ -group, -CH ₂ -O-CH ₂ -group, -CH ₂ CH ₂ -O-CH ₂ -group, -CH _{2
CH 2 -O-CH 2 CH 2} - _{group, -CH 2 CH 2 -O-CH} 2 CH 2 -O-CH 2 CH 2 - group, -CH
_{And a 2-} OC ₆ H ₄ -group. The ester bond represented by Z ₁ and Z _2, -COO- or -OCO-, and the like, also, as the amide bond, -CONH- or -
NHCO-.

As the fluorine-containing segment represented by Q, for example, the general formula [2]

[0015]

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[In the formula, Q ₁ and Q ₄ each independently represent an alkylene group, Q ₂ and Q ₃ each independently represent a fluorinated alkylene group, and Q ₅ represents an alkylene group or a fluorinated alkylene group. And p and s each independently represent 0 or a natural number (preferably a natural number of 1 to 2,000), and q and r each independently represent a natural number (preferably a natural number of 1 to 2,000)
Represents A fluorine-containing oxyalkylene group represented by the formula:

In the general formula [2], Q ₁ , Q ₄ and Q ₅
The alkylene group represented by may be linear, branched or cyclic, and includes, for example, an alkylene group having 1 to 10 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group, a butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2-ethylpropylene group, hexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, cyclopropylene group, cyclopropylene Examples thereof include a pentylene group and a cyclohexylene group, and preferably include a lower alkylene group having 1 to 6 carbon atoms. The fluorine-containing alkylene group represented by Q ₂ , Q ₃ and Q ₅ is a group in which at least one hydrogen atom of the alkylene group is fluorinated, and includes a group in which all hydrogen atoms are fluorinated. . As these fluorine-containing alkylene groups, hydrogen atoms of the alkylene group are fluorinated, for example, fluoromethylene group, fluoroethylene group, fluoroprolene group, fluorobutylene group, fluoropentylene group, fluorohexylene group, difluoromethylene group , Difluoroethylene group, difluoroprolene group, trifluoropropylene group, fluorocyclohexylene group, trifluoroethylene group, pentafluoroethylene group, perfluoropropylene group, perfluoro-2,2-dimethylpropylene group, perfluoro-2 -Ethylpropylene group, perfluorohexylene group, perfluorocyclopropylene group, perfluorocyclopentylene group, perfluorocyclohexylene group and the like. Preferred examples of these fluorinated alkylene groups include a perfluoroalkylene group having 1 to 6 carbon atoms.

The molecular weight of the fluorine-containing segment is appropriately selected usually from the range of 100 to 50,000, preferably 500 to 25,000, more preferably 1,000 to 10,000.

The polymerization degree n of the fluorine-containing macroazo compound composed of the repeating unit represented by the above general formula [1] of the present invention is usually 2 or more, preferably 2 to 100, more preferably 2 to 50. Is mentioned.

The production of the fluorine-containing macroazo compound comprising the repeating unit represented by the above general formula [1] of the present invention may be carried out, for example, as follows. That is,
For example, general formula [3]

[0021]

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And an appropriate fluorine-containing ether compound such as the general formula [4]

[0023]

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Can be obtained by reacting with a fluorine-containing ether compound represented by the formula (1) in a suitable solvent, if necessary, in the presence of a basic catalyst, and further, if necessary, in an inert gas atmosphere using a dehydrating agent. it can.

In the above formula, R ^{1 to} R ⁴ , A ₁ , A ₂ , T ₁ ,
T ₂ , Q _{1 to} Q ₅ , p, q, r and s are the same as described above. W ₁ and W ₂ , and Y ₁ and Y ₂ represent a combination of groups capable of reacting with each other to form an ester bond or an amide bond. For example, when one is a carboxyl group and the other is a hydroxyl group or an amino group, Examples include a case where one is a hydroxyl group and the other is a carboxyl group or an isocyanate group, a case where one is an amino group and the other is a carboxyl group, a case where one is an isocyanate group and the other is a hydroxyl group, and the like.

Examples of the reaction solvent include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and dimethoxyethane, and halogenated compounds such as carbon tetrachloride, chloroform, methylene chloride, ethane dichloride, tricrene and xylene hexafluoride. Examples of the hydrocarbon include hydrocarbons such as n-hexane, benzene, toluene, and xylene; esters such as ethyl acetate, butyl acetate and methyl propionate; acetonitrile; and N, N-dimethylformamide. These may be used alone or in combination of two or more.

The dehydrating agent is not particularly limited as long as it is used as a dehydrating condensing agent.
Diphosphorus pentoxide, inorganic dehydrating agents such as anhydrous zinc chloride, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, carbodiimides such as 1-ethyl-3- (3-dimethylaminopropylcarbodiimide) hydrochloride, polyphosphoric acid, acetic anhydride, carbonyl Diimidazole, p-toluenesulfonyl chloride and the like.

The amount of the dehydrating agent used is not particularly limited. However, if the amount is too small, the reaction becomes slow, and if the amount is too large, it is not economical. , Preferably in the range of 2 to 3 moles.

The above production method is preferably carried out in the presence of a basic catalyst. Specific examples of the basic catalyst include, for example, triethylamine, diisopropylethylamine, N, N-dimethylaniline, piperidine, pyridine, 4-dimethylamino Pyridine, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, tri
organic amines such as -n-butylamine and N-methylmorpholine; metal hydrides such as sodium hydride; and basic alkali metal compounds such as n-butyllithium and tert-butyllithium.

The amount of the basic catalyst used is usually 0.5 to 5 moles, preferably 1 to 5 moles per mole of the azo compound or dehydrating agent.
It is appropriately selected from the range of ~ 2 times mol.

The proportion of the azo compound and the fluorine-containing ether compound used in producing the fluorine-containing macroazo compound of the present invention is not particularly limited and may be appropriately determined.
It is preferable to use both in substantially equimolar amounts.

The above manufacturing method may be performed in an inert gas atmosphere. Examples of the inert gas include a nitrogen gas and an argon gas.

The reaction temperature is not particularly limited, but if it is too high, the azo group will be decomposed, and if it is too low, the reaction rate will be slow and the production will require time. Therefore, it is usually selected from the range of -10 to 60 ° C. The reaction temperature may be increased stepwise from a low temperature. The reaction time naturally varies depending on other reaction conditions, but is usually appropriately selected from the range of 1 to 60 hours.

The desired product may be isolated according to the type and amount of the starting materials, the basic catalyst, the dehydrating agent, the solvent, etc., and the state of the reaction solution. For example, in the case of a viscous reaction solution, Can be obtained by diluting the reaction solution with an appropriate solvent, removing impurities by an operation such as filtration or washing with water, and then removing the solvent to obtain the desired fluorine-containing macroazo compound.

The azo compound represented by the general formula [3] and the fluorine-containing ether compound represented by the general formula [4], which are used as raw materials, may be commercially available products or appropriately prepared by a conventional method. May be used.

In the fluorine-containing macroazo compound thus obtained, the azo group is easily decomposed by heating or light irradiation, and radical species are generated with the generation of nitrogen gas. At that time, if various monomers are present, polymerization is promptly caused.

The feature of the fluorine-containing macroazo compound of the present invention resides in that a fluorine-containing segment having a large amount of fluorine atoms is present as a constitutional unit in a molecule. When a block polymer is produced by using the above, a segment having a large amount of fluorine atoms can be efficiently introduced into the obtained block polymer.

The production of the fluorine-containing block polymer of the present invention using the fluorine-containing macroazo compound of the present invention as a macroazo initiator may be carried out, for example, as follows. That is, the above-mentioned general formula [1] obtained as described above
And a fluorine-containing macroazo compound represented by general formula [5]

[0039]

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[0040] (wherein, R ⁵ represents a hydrogen atom, a lower alkyl group or a halogen atom, R ⁶ represents a hydrogen atom, a lower alkyl group, a halogen atom, a carboxyl group, an alkyloxycarbonyl group or a formyl group, R ⁷ Is a hydrogen atom,
Represents a lower alkyl group, a carboxyl group, an alkyloxycarbonyl group or a halogen atom, R ⁸ represents an alkylene group or a bond which may have a double bond, R ⁹ represents a hydrogen atom, an alkyl group, a haloalkyl group, Aryl group,
Aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom,
Alkyloxycarbonyl group, aralkyloxycarbonyl group, hydroxyalkyloxycarbonyl group, aryloxycarbonyl group, acyloxy group, cyano group,
Represents a carboxyl group, formyl group, amino group, sulfonic acid group, carbamoyl group, and hydroxyl group. The polymerization reaction may be carried out with the monomer represented by the formula (1) in a suitable solvent or without a solvent, if necessary, in an inert gas atmosphere according to a conventional method. Post-treatment after the reaction may be carried out in accordance with a post-treatment method generally used in this field.

When conducting the polymerization reaction, a chain transfer agent (for example, lauryl mercaptan, octyl mercaptan, butyl mercaptan, 2-mercaptoethanol, butyl thioglycolate, etc.) is added as necessary to control the molecular weight. You may go.

The method of the above polymerization reaction includes, for example, suspension polymerization, solution polymerization, bulk polymerization and emulsion polymerization. At this time, the fluorine-containing macroazo compound and a usual radical polymerization initiator (for example, azobisisobutyronitrile, 2,
Dimethyl 2'-azobisisobutyrate).

In the general formula [5], examples of the halogen atom represented by R ⁵ , R ⁶ , R ⁷ and R ⁹ include fluorine, chlorine, bromine and iodine. The lower alkyl group represented by R ⁵ , R ⁶ and R ⁷ may be linear or branched and includes, for example, an alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group,
Neopentyl group, tert-pentyl group, 3,3-dimethylbutyl group, 1,1-dimethylbutyl group, 1-methylpentyl group, n
-Hexyl group, isohexyl group and the like. R ⁶ , R
^The alkyloxycarbonyl group represented by ⁷ and R ⁹ may be linear or branched, and may have a double bond, for example, an alkyloxycarbonyl group having 2 to 19 carbon atoms. Specifically, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group Octadecyloxycarbonyl group, ethenyloxycarbonyl group, propenyloxycarbonyl group, butenyloxycarbonyl group,
Examples include a tert-butyloxycarbonyl group and a 2-ethylhexyloxycarbonyl group. The alkyl group represented by R ⁹ may be linear, branched, or cyclic, and may have a double bond. Examples thereof include an alkyl group having 1 to 20 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl , 3,3-dimethylbutyl, 1,1-dimethylbutyl, 1-methylpentyl, n-hexyl, isohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl Group, octadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group And the like. Examples of the haloalkyl group include a haloalkyl group having 1 to 20 carbon atoms in which the above alkyl group is halogenated (for example, fluorinated, chlorinated, brominated, iodinated, etc.), and specifically, a chloromethyl group, Bromomethyl group, trifluoromethyl group,
2-chloroethyl group, 3-chloropropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 2-perfluorooctylethyl group, perfluorooctyl group, 1-chlorodecyl group, 1-chlorooctadecyl And the like.
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a 4-methylphenyl group, a 4-ethylphenyl group, a 4-methoxyphenyl group, a 4-methoxyphenyl group.
Examples include a vinylphenyl group, a 4-chlorophenyl group, an aminophenyl group, a hydroxyphenyl group, and a carboxyphenyl group. As the aliphatic heterocyclic group, for example, a 5- or 6-membered aliphatic heterocyclic group is preferable, and those containing 1 to 3 hetero atoms such as a nitrogen atom, an oxygen atom, and a sulfur atom as isomer atoms are preferable. Examples thereof include, for example, a pyrrolidyl-2-one group, a piperidino group,
Examples include a piperazinyl group and a morpholino group. As the aromatic heterocyclic group, for example, a 5- or 6-membered aromatic heterocyclic group is preferable, and those containing 1 to 3 hetero atoms such as nitrogen, oxygen, and sulfur as isomer atoms are preferable. Specific examples thereof include a pyridyl group, an imidazolyl group, a thiazolyl group, a furanyl group, and a pyranyl group. Examples of the aralkyloxycarbonyl group include an aralkyloxycarbonyl group having 8 to 20 carbon atoms, and specific examples include a benzyloxycarbonyl group and a phenethyloxycarbonyl group. Examples of the acyloxy group include, for example, an acyloxy group having 2 to 18 carbon atoms derived from a carboxylic acid. Group, octanoyloxy group,
Examples include a lauroyloxy group, a stearoyloxy group, and a benzoyloxy group. Examples of the hydroxyalkyloxycarbonyl group include a hydroxyalkyloxycarbonyl group having 2 to 19 carbon atoms in which a hydrogen atom of the alkyloxycarbonyl group is substituted with a hydroxyl group as described above, specifically, a hydroxymethyloxycarbonyl group, Hydroxyethyloxycarbonyl, hydroxypropyloxycarbonyl, hydroxybutyloxycarbonyl, hydroxypentyloxycarbonyl, hydroxyhexyloxycarbonyl, hydroxyheptyloxycarbonyl, hydroxyoctyloxycarbonyl, hydroxydodecyloxycarbonyl, hydroxyoctadecyl An oxycarbonyl group; As the aryloxycarbonyl group,
Examples thereof include an aryloxycarbonyl group having 7 to 20 carbon atoms, and specific examples include a phenyloxycarbonyl group and a naphthyloxycarbonyl group. The alkylene group which may have a double bond represented by R ⁸ may be linear or branched and has, for example, 1 to 10 carbon atoms.
Examples of the alkylene group having a double bond include one or more, preferably 1 to 5 double bonds at the terminal of the alkylene group or at any position in the chain.
More preferably, those having 1 to 3 groups, specifically, methylene group, ethylene group, propylene group, butylene group, 2-methylpropylene group, pentylene group, 2,2-dimethylpropylene group, 2 -Ethylpropylene, hexylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, ethenylene, propenylene, butenylene, pentenylene, hexenylene, butadienylene and the like.

Specific examples of the monomers used for producing the fluorine-containing block polymer of the present invention include, for example, styrene, 4-methylstyrene, 4-ethylstyrene,
8-20 carbon atoms such as methoxystyrene and divinylbenzene
Α-ethylenic aromatic hydrocarbons such as vinyl formate, vinyl acetate, vinyl propionate, and isopropenyl acetate having 3 to 20 carbon atoms such as vinyl chloride, vinylidene chloride, vinylidene fluoride and tetrafluorocarbon 2 to 2 carbon atoms such as ethylene and tetrachloroethylene
20 halogen-containing vinyl compounds such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, vinyl acetic acid, allyl acetic acid, vinyl benzoic acid, etc. Ethylenic carboxylic acids (these acids may be in the form of a salt such as an alkali metal salt such as sodium or potassium or an ammonium salt), such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, or methacrylic acid Butyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, vinyl methacrylate, allyl methacrylate, phenyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate , Acrylic acid Urile, stearyl acrylate,
Vinyl acrylate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, methyl crotonate, ethyl crotonate, vinyl crotonate, dimethyl citraconic acid, diethyl citraconic acid, mesaconic acid Dimethyl, diethyl mesaconate, methyl 3-butenoate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, acrylic acid 2 -4-20 carbon atoms such as hydroxypropyl
Ethylenic carboxylic acid esters such as acrylonitrile, methacrylonitrile, allyl cyanide and the like containing cyanovinyl compounds having 3 to 20 carbon atoms, for example, acrylamide and methacrylamide such as vinyl amide compounds having 3 to 20 carbon atoms, For example, ethylenic aldehydes having 3 to 20 carbon atoms such as acrolein and crotonaldehyde, and vinyl sulfonic acids having 2 to 20 carbon atoms such as vinyl sulfonic acid and 4-vinylbenzene sulfonic acid (these acids include, for example, sodium, potassium and the like) May be in the form of a salt such as an alkali metal salt of).
Vinyl aliphatic amines having 2 to 20 carbon atoms such as allylamine, for example, vinyl aromatic amines having 8 to 20 carbon atoms such as vinylaniline, for example, 5 to 20 carbon atoms such as N-vinylpyrrolidone and vinylpiperidine. Vinyl aliphatic heterocyclic amines, for example, vinyl aromatic heterocyclic amines having 5 to 20 carbon atoms such as vinylpyridine and 1-vinylimidazole, and ethylene having 3 to 20 carbon atoms such as allyl alcohol and crotyl alcohol Alcohols, for example, ethylenic phenols having 8 to 20 carbon atoms such as 4-vinylphenol, for example, 4 to 20 carbon atoms such as butadiene and isoprene;
Diene compounds. These may be used alone or in combination of two or more.

In the fluorine-containing block polymer obtained by subjecting a monomer to a polymerization reaction in the presence of the fluorine-containing macroazo compound according to the present invention, the composition ratio of the unit derived from the fluorine-containing macroazo compound is not particularly limited. Although not particularly limited, it is usually appropriately selected from the range of 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight.

The constituent ratio of the monomer unit is not particularly limited, but is appropriately selected from the range of usually 99 to 1% by weight, preferably 95 to 5% by weight, more preferably 90 to 10% by weight. Is done.

The concentration of the fluorine-containing macroazo compound and the monomer during the polymerization reaction is usually 5 to 10
It is appropriately selected so as to be in a range of 0% by weight (without solvent), preferably 10 to 100% by weight (without solvent).

The polymerization reaction is preferably performed in the presence of an organic solvent. Examples of the organic solvent include hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane, and n-octane, such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and the like.
Halogenated hydrocarbons such as xylene hexafluoride, for example, esters such as methyl acetate, ethyl acetate, n-butyl acetate, and methyl propionate, for example, carboxylic acids such as fluoroacetic acid, trifluoroacetic acid, and trifluoroacetic anhydride, for example, Ketones such as acetone, methyl ethyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol; N-methylpyrrolidone , N, N-dimethylacetamide, dimethylsulfoxide and the like. These may be used alone or in combination of two or more. When the fluorine-containing polymer according to the present invention is used as a cosmetic base, if an alcohol such as ethanol or isopropanol is used as a solvent, the residual solvent may affect the human body or be used as a base directly after the reaction. It is preferred in terms of.

The polymerization reaction is desirably carried out in an inert gas atmosphere. Examples of the inert gas include a nitrogen gas and an argon gas.

The polymerization temperature is not particularly limited. If the polymerization temperature is too low, the progress of polymerization is slow because the decomposition of the azo group is small, and if it is too high, the decomposition of the azo group becomes too large and the control of the polymerization becomes difficult. The temperature is appropriately selected from the range of 150 ° C, preferably 40 to 120 ° C. The reaction time varies depending on the reaction conditions such as the reaction temperature, the type of the fluorine-containing macroazo compound and the monomer to be reacted, or the concentration, but is usually 2 to 3.
It is appropriately selected from a range of 24 hours.

The molecular weight of the fluorine-containing block polymer thus obtained is not particularly limited, but the number average molecular weight is usually 3,000 or more, preferably 5,000 to 200.
And more preferably 10,000 to 1.5 million.

The fluorine content in the fluorine-containing block polymer is usually 0.1 to 90%, preferably 1 to 7%.
It is appropriately selected from the range of 5%.

The polymer compound is not necessarily unique because it generally has a complicated structure. However, when the fluorine-containing block polymer of the present invention is intentionally represented by the structural formula, it is represented by the repeating unit represented by the general formula [1]. Since the polymerization reaction is carried out using the constituted fluorine-containing macroazo compound as a macroazo initiator, for example, the following general formula [6]
And the like.

[0054]

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[Wherein U represents a fluorine-containing unit;
Represents a monomer unit, a represents a natural number, and b represents an integer of 2 or more. The symbols in the squares are random structures, and include various structures such as copolymers of a graft type, a block type and the like. ]

In the general formula [6], the fluorine-containing unit represented by U is a unit derived from the fluorine-containing macroazo compound represented by the general formula [1] of the present invention.
For example, those represented by the following general formula [1a] can be mentioned.

[0057]

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(Where R ^{1 to} R ⁴ , A ₁ , A ₂ , Z ₁ , Z ₂ ,
T ₁ , T ₂ and Q are the same as above. )

The monomer unit represented by V is derived from the monomer represented by the above general formula [5]. Examples of the monomer unit include those represented by the following general formula [5a]. No.

[0060]

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(In the formula, R ^{5 to} R ⁹ are the same as described above.)

The fluorine-containing block polymer thus obtained has excellent effects such as water repellency, oil repellency, heat resistance, weather resistance, chemical resistance, antifouling property and adhesiveness. As a polymer for a resin composition such as a resin composition for coating and a resin composition for coating, for example, a base for cosmetics such as a base for hair cosmetics (for example, a setting agent, a treatment agent, etc.), a base for basic cosmetics, etc. Or as a release agent, a coating agent, a surface modifier, a medical material, an anti-adhesion agent, a deodorant, and the like.

The fluorine-containing block polymer of the present invention comprises
When the monomer is a water-soluble compound, the obtained fluorine-containing block polymer can be water-soluble, and thus can be effectively used for applications such as water-soluble paints. Also,
When the monomer is an oil-soluble compound, the resulting fluorine-containing block polymer is rich in water repellency and the like, and thus can be effectively used for applications such as oil-soluble paints.

When the fluorine-containing block polymer of the present invention is used in, for example, a resin composition for coating or coating, examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, for example, acetone, methyl ethyl ketone and the like. Ketones such as ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and dimethoxyethane; lower alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, sec-butanol; and ethyl acetate, butyl acetate; Esters such as methyl propionate and the like.

When the fluorine-containing block polymer of the present invention is used as the above resin composition, other components may be added as necessary. Components that can be added include, for example, pigments, fillers, aggregates, defoamers, plasticizers, rust inhibitors, film-forming auxiliaries, ultraviolet absorbers, thickeners, release agents, dyes, and the like.

Some of the fluorine-containing block polymers of the present invention are also excellent in solubility in water and ethanol. When this is used as a base for hair cosmetics, moisture resistance, setting power , Elasticity, flaking,
It has the potential to be a base excellent in various functions required as a base for hair cosmetics such as texture.

When the fluorine-containing block polymer of the present invention is dissolved in a hydrophilic organic solvent and used as a base for cosmetics, examples of the hydrophilic organic solvent include various lower alcohols and glymes. In consideration of the influence of, for example, ethanol, isopropanol and the like are more preferable.

When the fluorine-containing block polymer of the present invention is used as a cosmetic base, other cosmetic ingredients may be added as long as the function is not impaired. Components that can be added include, for example, surfactants, fats and oils, sugars, acids, bases, buffers, salts, water, alcohols, protein derivatives,
Examples include crude drugs, propellants, preservatives / disinfectants, antioxidants, ultraviolet absorbers, sequestering agents, oxidants, reducing agents, pigments, fragrances, and the like.

The fluorine-containing block polymer of the present invention comprises
When the monomer is a water-soluble compound, the obtained fluorine-containing block polymer becomes soluble in water or alcohol, for example, a set type, a hairdressing material such as a treatment type, and a treatment agent having a volume down effect and the like. It can be expected to be used as a base for hair cosmetics, and when the monomer is an oil-soluble compound,
When the obtained fluorine-containing block polymer is used as a base for hair cosmetics, it forms a tough film,
The effect of improving water repellency, surface glossiness and dirt removal by the fluorine segment on the surface can be expected. Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Experimental Examples, but the present invention is not limited thereto.

[0070]

【Example】

Embodiment 1 FIG. Synthesis of Fluorine-Containing Macroazo Compound Fomblin E (fluorinated polyoxyalkylene. Both ends are hydroxyl groups. Weight average molecular weight: about 230
0. 22.0 g of dicyclohexylcarbodiimide (DCC), 1.2 g of 4-dimethylaminopyridine (DMAP) and 2.8 g of 4,4′-azobis (4-cyanopentanoic acid) in 20 ml of m-xylene hexafluoride The suspension was suspended in a mixed solvent of 30 ml of methylene chloride and reacted with stirring at 20 to 25 ° C. for 8 hours. After standing overnight, the precipitated crystals were removed by filtration, and the filtrate was poured into 500 ml of methanol to precipitate the fluorine-containing macroazo compound. This was separated and dried under reduced pressure to obtain the intended fluorine-containing macroazo compound 20.3
g (yield 84.5%). ^{1 H-NMR δppm ((CF} 3 CO) 2 O): 1.67 (s, 3H, C H
_{3), 1.77 (s, 3H} , C H 3), 2.35~2.6 (m, 8H, NCC H 2 C H 2 -
CO), 3.85 (brs, 8H , COO-CH 2 C H 2 O, OC H 2 CH 2), 4.30 (b
rs, 4H, COO-C H 2 CH 2). ^{IR: 1740cm -1 (COO),} 1209cm -1 (-CF 2 -).

Embodiment 2 FIG. Production of Fluorine-Containing Block Polymer Fluorine-Containing Macroazo Compound Obtained in Example 1 5.0
g, 20 g of methyl methacrylate (hereinafter abbreviated as MMA) and 60 ml of m-xylene hexafluoride were mixed and polymerized at 70 ° C. for 5 hours in a nitrogen stream. After completion of the reaction, the reaction solution was poured into 1 L of methanol to precipitate a fluorine-containing block polymer. This is collected by filtration and dried to obtain the desired white blocky fluorine-containing block polymer 2
2.8 g (91.1% yield) were obtained. From the GPC measurement results,
Its number average molecular weight is 59,400 and its weight average molecular weight is
This was a fluorine-containing block polymer having a dispersion degree of 126,000 and a dispersity of 2.12. Hereinafter, this is abbreviated as polymer F1.

Embodiment 3 FIG. Preparation of Fluorine-Containing Block Polymer In Example 2, the polymerization reaction was carried out in exactly the same manner as in Example 2 except that styrene was used instead of MMA, and the desired slightly yellow powdery fluorine-containing block polymer 20.1 g was obtained.
(80.2% yield). Hereinafter, this is abbreviated as polymer F2.

Experimental Example 1 Polymer F obtained in Example 2
11 g was placed in a volumetric flask, and chloroform was added and dissolved to make a total volume of 10 ml. Next, a film obtained by casting the obtained solution on a glass petri dish is dried under reduced pressure, and then FACE CONTACT-ANGLE METER CA-D [Kyowa Interface Science
Co., Ltd. ] To measure the contact angle with water. Table 1 shows the results
Shown in

Experimental Example 2 In Experimental Example 1, polymer F
After casting in exactly the same manner as in Experimental Example 1 except that Polymer F2 was used in place of 1, the contact angle with water was measured.
The results are shown in Table 1.

Comparative Example 1 The polymerization reaction was carried out in the same manner as in Example 2 except that 0.14 g of azobisisobutyronitrile (AIBN) was used in place of 1.0 g of the fluorine-containing macroazo compound obtained in Example 1. Then, white mass polymethyl methacrylate (hereinafter, PM
Abbreviated as MA. 43.7 g (43.6% yield). G
From the results of the PC measurement, the number average molecular weight of this product was 68,00
0, the weight average molecular weight was 121,000, and the dispersity was 1.77. 1 g of the obtained PMMA was placed in a volumetric flask, and chloroform was added and dissolved to make a total volume of 10 ml.
Next, after casting the obtained solution on a glass petri dish, FACE CONTACT-ANGLE METER CA-D [Kyowa Interface Science
Co., Ltd. ] To measure the contact angle with water. Table 1 shows the results
Shown in

[0076]

[Table 1] 1) The film formability was evaluated by visual inspection to see whether or not a film was uniformly formed on each glass petri dish surface.

From the above results, in Experimental Examples 1 and 2, the contact angle with water of the film obtained by casting on a glass petri dish was improved as compared with that of the glass itself.
It is understood that the water repellency of glass can be improved by the fluorine-containing block polymer of the present invention. Also, compared to the film cast with PMMA in Comparative Example 1,
Since the films obtained by casting the fluorine-containing block polymer of the present invention in Experimental Examples 1 and 2 have a large contact angle with water and high water repellency, the fluorine-containing block polymer of the present invention is higher than PMMA. For example, it is apparently excellent as a resin composition such as a paint or a base for cosmetics.

Experimental Example 3 Solubility test The polymer F1 obtained in Example 2 was placed in a volumetric flask, and various solvents were added to conduct a solubility test. Table 2 shows the results.

[0079]

[Table 2] 1) MEK: methyl ethyl ketone 2) THF: tetrahydrofuran 3) Ph (CF ₃ ) ₂ : xylene hexafluoride 4) HFIP: hexafluoroisopropanol

From the results in Table 2, it can be seen that the conventional polymer having a fluorine segment had a problem in solubility, but the fluorine-containing block polymer of the present invention was excellent in solubility.

[0081]

As described above, the present invention provides a fluorine-containing macroazo compound having a segment having a large amount of fluorine atoms in a molecule, and a polymerization reaction using the fluorine-containing macroazo compound as a macroazo initiator. By carrying out the above, a large amount of fluorine atoms can be efficiently introduced into the polymer, which is a great invention that contributes to the industry.

Claims (7)

[Claims] 1. A compound of the general formula [1] (Wherein, R ¹ and R ³ each independently represent a lower alkyl group, R ² and R ⁴ each independently represent a lower alkyl group or a cyano group, and A ₁ and A ₂ each independently represent Represents an oxygen atom and / or a lower alkylene group which may be via an aromatic ring, Z ₁ and Z ₂ each independently represent an ester bond or an amide bond, and T ₁ and T ₂ each independently represent , -CO
NH represents a bond or a bond, and Q represents a fluorine-containing segment. A) a fluorine-containing macroazo compound composed of repeating units represented by the formula: 2. The polymerization degree is 2 or more and 100 or less.
3. The fluorine-containing macroazo compound according to item 1. 3. A compound represented by Q in the general formula [1],
3. The fluorine-containing macroazo compound according to claim 1, wherein the fluorine-containing segment is a fluorine-containing oxyalkylene group. 4. A method for polymerizing a monomer, comprising using the fluorine-containing macroazo compound according to claim 1. 5. A macroazo initiator comprising the fluorine-containing macroazo compound according to claim 1. 6. A fluorine-containing block polymer obtained by polymerizing a monomer using the fluorine-containing macroazo compound according to claim 1. 7. A fluorine-containing block polymer comprising a unit derived from the fluorine-containing macroazo compound according to claim 1 and a monomer unit as constituent components.