JP3346486B2 - Method for producing fluorine-containing block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel and useful fluorine-containing block copolymer.

[0002]

2. Description of the Related Art It has long been known that block copolymers have different properties from random copolymers, and many studies have been reported on their synthesis methods. Since these block copolymers have two types of polymer segments having completely different properties in the same molecule, they exhibit surface localization phenomena and interface localization phenomena derived therefrom.

In response to the recent sophistication of market needs, materials having high weather resistance and stain resistance have been developed utilizing the above properties of the block copolymer. For example, JP-A-2-240121 reports a method in which the excellent properties of a fluorine compound are applied to a block copolymer for synthesizing a resin having a high degree of weather resistance. There were problems in the synthesis, such as the inability to heat during the synthesis of the block copolymer, and associated problems, such as a low degree of freedom in combining block segments.

[0004] On the other hand, German Offenlegungsschrift No. 3833651 reports a method of synthesizing a block copolymer with less restrictions in terms of synthesis by using a method utilizing photopolymerization. With polymers, the high weather resistance and stain resistance required by the market cannot be fully exhibited,
It was not practical.

[0005]

That is, there has been no method for obtaining a copolymer which gives a film having a high degree of freedom in production conditions and a high degree of weather resistance and stain resistance.

[0006]

Means for Solving the Problems Accordingly, the inventors of the present invention have conducted intensive studies in view of the current state of various drawbacks in the prior art as described above. As a result, they are inactive in a heated state, but undergo polymerization under light irradiation. In the presence of a compound having a functional group capable of initiating, a copolymer that gives a film having high weather resistance and stain resistance if it is photopolymerized with a fluorine-containing vinyl monomer as an essential monomer However, they have found that they can be obtained more easily than the conventional method, and have completed the present invention.

That is, the present invention relates to a method for producing a polymer having a terminal functional group capable of initiating photopolymerization by irradiating one or both ends of a polymer chain with light having a wavelength of 200 to 450 nm. An object of the present invention is to provide a method for producing a fluorine-containing block copolymer, which comprises photopolymerizing a fluorovinyl monomer (II) as an essential monomer.
Hereinafter, this method for producing a novel fluorine-containing block copolymer is simply referred to as the method of the present invention.

According to the method of the present invention, it is possible to provide a fluorine-containing block copolymer which exhibits higher performance required by the market and has less restrictions on the synthesis surface of the block copolymer and the combination surface of the block segments. I can do it.

According to the present invention, one or both ends of a polymer chain are irradiated with light having a wavelength of 200 to 450 nm to initiate photopolymerization, and the compound (I) having a terminal functional group is contained in the presence of the compound. Since the fluorovinyl monomer (II) is polymerized, a segment derived from the compound (I), which has been well known, or is new or has been conventionally difficult, is compounded with the monomer (II) as the compound (I). ) Can be provided with good reproducibility.

One major compound (I) in the method of the present invention has a wavelength of 20 at one or both ends of a polymer chain.
A compound having a terminal functional group capable of initiating photopolymerization by irradiating light of 0 to 450 nm. Hereinafter, this is referred to as a polymer photoinitiator.

One or two terminal functional groups capable of photopolymerizing a vinyl monomer are bound to the terminal of the polymer chain in the polymer photoinitiator. In the method of the present invention, the initiator is a polymer chain having a linear or almost linear polymer chain having one or two terminal functional groups instead of a branched structure as a polymer chain. Preferably it is an initiator.

In the method of the present invention, the polymer chain in the polymer photoinitiator may be any of an oligomer, a polymer and a high polymer. The choice of which of these to use may be determined according to the properties of the desired product, ie, the block copolymer.

The number average molecular weight of the polymer chain in the polymer photoinitiator in the method of the present invention is not particularly limited, but may be 200 or less.
To 500,000, preferably 400 to 200,000. The polydispersity (Mw / Mn) of the polymer chains in the polymer photoinitiator in the process according to the invention is approximately or exactly 1 to 1
It may be between 0 and a dispersion having one peak, two peaks or more in the molecular weight distribution. Suitable polydispersities for the process according to the invention are preferably from 1 to 6,
It is a molecular weight distribution of a peak. However, a polymer chain having a molecular weight distribution of two peaks or more can be applied in order to express special properties.

The polymer chain in the polymer photoinitiator in the method of the present invention may be any of a homopolymer, a random copolymer, an alternating copolymer or a block copolymer. Usually, this polymer chain is often synthesized using various different monomers.

Examples of the homopolymer, random copolymer, alternating copolymer or block copolymer which can be used as the polymer chain in the polymer photoinitiator in the method of the present invention include, for example, polyurethanes Polyesters; polyolefins such as polyethylene, polypropylene, ethylene vinyl acetate copolymer, ethylene propylene copolymer, polybutylene-1, polyisobutylene or poly-4-methylpentene-1; polybutadiene, polyisoprene, butadiene isoprene copolymer Polydienes such as styrene butadiene copolymer, styrene butadiene styrene block copolymer or styrene isoprene styrene block copolymer; polyethylene oxide, polypropylene oxide or polyethylene propylene oxide. It can polyalkylene oxides; such 含硅 containing polymer polydimethylsiloxane; such polyamides as nylon 6,11,12,66 or 610; polycarbonates and the like.

Further, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl Isononyl acid, decyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylic acid Various (meth) acrylates such as 2-butoxyethyl, cyclohexyl (meth) acrylate or benzyl (meth) acrylate; various aromatic vinyl monomers such as styrene, α-methylstyrene or p-methylstyrene; Vinylpyridine, vinylimidazole, vinylpyrrolidone or Such heterocycle-containing vinyl monomers vinylcarbazole; (meth) acrylamide or N
-Various amide bond-containing vinyl monomers such as methoxymethyl (meth) acrylamide; (meth) acrylonitrile, vinyl acetate and the like, or (meth) acrylic acid,
Carboxyl group-containing vinyl monomers such as crotonic acid, maleic acid, fumaric acid or itaconic acid; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate or β-methylglycidyl (meth) acrylate; Diesters of an unsaturated dicarboxylic acid such as fumaric acid and a C1 to C18 monohydric alcohol; tetrafluoroethylene, hexafluoropropylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene Α-olefins containing fluorine such as pentafluoropropylene or hexafluoropropylene; or trifluoromethyltrifluorovinylether, pentafluoroethyltrifluorovinylether or hepta (Per) fluoroalkyl perfluorovinyl ethers having 1 to 18 carbon atoms in a (per) fluoroalkyl group such as fluoropropyltrifluorovinyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2 3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5
H-octafluoropentyl (meth) acrylate, 1
(Per) fluoroalkyl (meth) having 1 to 18 carbon atoms in a (per) fluoroalkyl group such as H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Acrylates; and homopolymers or copolymers obtained by polymerizing monomers such as vinyl monomers.

In the synthesis of the polymer chain in the polymer photoinitiator in the method of the present invention, there is no special point in terms of methodologies, and compounds which can be synthesized by common known methods, available industrial products, etc. Can be used, the above-mentioned known monomer radical, cation, anion homopolymerization, copolymerization,
It can be synthesized by block copolymerization or known polycondensation, polyaddition or addition condensation. Of course, the polymerization means may be either thermal polymerization or photopolymerization.

In the method of the present invention, the terminal functional group bonded to the polymer chain in the polymer photoinitiator is from 200 to 450.
It is necessary that the monomer can be polymerized by irradiation with light of nm.

That is, the terminal functional group can be said to be one or two photopolymerization initiators bonded to the polymer chain. In principle, all terminal functional groups having such properties can be used in the present invention. The choice of the terminal functional group applied here depends on the nature of the monomer mixture to be photopolymerized. Therefore, the terminal functional groups suitable for the method according to the present invention are inactive at the time of heating in a dark place, start photopolymerization of the monomer mixture by irradiating light, and are unnecessary with other functional groups contained in the reaction system. It is preferable to select a substance that does not cause a serious side reaction.

The terminal functional group of the initiator of the process according to the invention consists of two parts as represented by the general formula: One is a true photopolymerization initiation group portion (A), and the other is a portion (B) for bonding a photopolymerization initiation group to a terminal of a polymer chain in a polymer photoinitiator.

... Polymer chain ...- (B)-(A)

The true photoinitiator moiety (A) in the terminal functional group suitable for the method of the present invention is not particularly limited, and can be derived from a known photopolymerization initiator. That is, the difference between the known photopolymerization initiator and the photopolymerization initiator of the terminal functional group is merely whether or not it is bonded to the terminal of the polymer chain in the polymer initiator.

Examples of the true photopolymerization initiating moiety (A) in the terminal functional group suitable for the method of the present invention include a terminal functional group having a structure represented by the following formula.

[0024]

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Further, specific examples of the true photopolymerization initiation group portion (A) in the terminal functional group which are more suitable for the method according to the present invention include at least one type of moiety (A) selected from the following group:
It has.

[0026]

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(Wherein, R 1 and R 2 represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxymethyl group or an alkoxymethyl group having 1 to 4 carbon atoms. R3 may be the same or different, and R3 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxymethyl group, an alkoxymethyl group having 1 to 4 carbon atoms, or a Represents 12 alkanoyl groups.)

[0028]

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(Wherein, R 4 is a hydrogen atom, carbon number 1)
Represents a hydrocarbon group having 1 to 12 carbon atoms or an alkoxymethyl group having 1 to 4 carbon atoms. R5 and R6 represent a substituted or unsubstituted phenyl group, which may be the same or different.
N is an integer of 0 to 4. )

[0030]

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(Wherein R 7 and R 8 represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms or an alkanoyl group having 1 to 12 carbon atoms, which may be the same or different. R 9 is substituted or Represents an unsubstituted phenyl group).

True photopolymerization initiating group (A) in terminal functional group
Is connected to the terminal of the polymer chain in the polymer photoinitiator in the method according to the present invention by a portion (B) having a role of binding the polymer chain.

The part (B) in the terminal functional group in the method of the present invention includes, for example, an organic, inorganic, or organometallic bond, and includes a true photopolymerization initiator (A) and a polymer photoinitiator. Those which are connected to the terminal of the polymer chain and are stable in each reaction condition and step of the method of the present invention can be preferably used. It is particularly preferable that the bonding portion (B) does not cause unnecessary side reactions, does not inhibit photopolymerization, and can be synthesized by a simple method under mild conditions.

Examples of the bonding moiety (B) suitable for the method of the present invention include, for example, urethane bond, ester bond, ether bond, thioether bond, amino bond, amide bond,
Urea bond, carbonyl bond, carbonate bond, sulfonate bond, phenylene bond, methylene bond having 1 to 10 carbon atoms, oxymethylene bond having 1 to 10 carbon atoms,
Examples thereof include an oxyethylene bond having 1 to 10 carbon atoms or an oxypropylene bond having 1 to 10 carbon atoms.

The second main compound in the method of the present invention is a fluorine-containing vinyl monomer (II). It is. As the monomer (II), a vinyl monomer having one unsaturated double bond is suitable.

In carrying out the method of the present invention, even if only the monomer (II) is photopolymerized in the presence of the compound (I), the monomer (II) may be copolymerized with another vinyl copolymer. Photopolymerization may be carried out in the presence of the compound (I) using a combination of monomers. Usually, as in the latter case, the monomer (II) is used together with another vinyl monomer copolymerizable therewith, and photopolymerized in the presence of the compound (I).

In the method of the present invention, one unsaturated 2
The fluorine-containing vinyl monomer having a double bond includes one, two, three, or more fluorine-containing vinyl monomers having two or three or more photopolymerizable unsaturated double bonds. A vinyl monomer other than a fluorine-containing vinyl monomer having a photopolymerizable unsaturated double bond can be used in combination.

Among them, regarding the purpose of the method of the present invention,
It is suitable to use a fluorine-free vinyl monomer having one unsaturated double bond in combination with a fluorine-containing vinyl monomer having one unsaturated double bond. Whether it is a fluorine-containing vinyl monomer or a fluorine-free vinyl monomer,
Because a vinyl monomer having three or more unsaturated double bonds alone results in a highly crosslinked product,
It is preferable to use mainly a vinyl monomer having one photopolymerizable unsaturated double bond, or use only the vinyl monomer.

However, this does not exclude vinyl monomers having two, three or more unsaturated double bonds from the scope of the process according to the invention. Conversely, they can be used for the purpose of modifying the properties of a product consisting of a vinyl monomer having one double bond. These two, three
Using a vinyl monomer having one or more double bonds, branched and. Alternatively, a crosslinked block copolymer can be synthesized.

[0040] Vinyl monomers (II) well suited for the process of the present invention include, for example, vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene. Fluorine-containing α-olefins such as propylene; or a (per) fluoroalkyl group such as trifluoromethyltrifluorovinylether, pentafluoroethyltrifluorovinylether or heptafluoropropyltrifluorovinylether having 1 to 18 carbon atoms (per) Fluoroalkyl perfluorovinyl ethers; 2,2,2
-Trifluoroethyl (meth) acrylate, 2,2
3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) And (per) fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in the (per) fluoroalkyl group such as acrylate.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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The above-mentioned fluorine-containing vinyl monomer (I)
Of course, I) may be used alone or in combination of two or more.

Other vinyl monomers which can be copolymerized with the fluorine-containing vinyl monomer (II) and which are suitable for the method of the present invention include, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether and isopropyl vinyl ether. , N-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether or phenylethyl vinyl ether. Alkyl vinyl ethers or substituted alkyl vinyl ethers; cyclopentyl vinyl ether and cyclohexyl vinyl ether; Ku cycloalkyl vinyl ethers such as methyl cyclohexyl vinyl ether; 2-
Hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-
Vinyl ethers having a hydroxyl group such as methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether or 6-hydroxyhexyl vinyl ether; vinyl-2,2-dimethylpropanoate, vinyl-2,
2-dimethylbutanoate, vinyl-2,2-dimethylpentanoate, vinyl-2,2-dimethylhexanoate, vinyl-2-ethyl-2-methylbutanoate,
Vinyl-2-ethyl-2-methylpentanoate, vinyl-3-chloro-2,2-dimethylpropanoate, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl caproate, capryl Acid vinyl,
Aliphatic vinyl carboxylate such as vinyl caprate, vinyl caprate, vinyl laurate, C9 branched aliphatic carboxylate, C10 branched aliphatic carboxylate, C11 branched aliphatic carboxylate or vinyl stearate Vinyl esters of carboxylic acids having a cyclic structure such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinylbenzoate or vinyl p-tert-butylbenzoate; methyl (meth) acrylate, ethyl (meth) acrylate ,
N-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, methyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acryl Isononyl acid, decyl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylic acid Various (meth) acrylates such as 2-butoxyethyl, cyclohexyl (meth) acrylate or benzyl (meth) acrylate; various aromatic vinyl monomers such as styrene, α-methylstyrene, divinylbenzene or p-methylstyrene Body; vinylpyridine, vinylimidazole, vinyl Heterocycle-containing vinyl monomers such as pyrrolidone or vinyl carbazole; (meth) acrylamide or N- methoxymethyl (meth) amide bond-containing vinyl monomers such as various acrylamide;
(Meth) acrylonitrile or carboxyl group-containing vinyl monomers such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; glycidyl (meth) acrylate or β-methylglycidyl (meth) acrylate Epoxy group-containing vinyl monomers; diesters of an unsaturated dicarboxylic acid such as maleic acid or fumaric acid with a C1 to C18 monohydric alcohol; various halogenated olefins other than fluoroolefins such as vinyl chloride or vinylidene chloride;
Alkadienes such as butadiene or isoprene;
And the like.

Further, a monomer having the following structure can be preferably used.

[0058]

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[0059]

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The mixing ratio of the above-mentioned fluorine-containing vinyl monomer (II) to another vinyl monomer copolymerizable with the fluorine-containing vinyl monomer is not particularly limited. It may be mixed and used so that the body has a composition capable of expressing desired physical properties within the range of 100 to 0.01% by weight.

The two main compounds described above in the method of the present invention, the polymer photoinitiator and the vinyl monomer (II) to be polymerized using the same, are mixed in an appropriate mixing ratio.

An appropriate mixing ratio of the two main compounds is not particularly limited, but is usually a mixing ratio exactly or approximately equal to the composition ratio of the block copolymer to be produced. The method of mixing the two main compounds is not particularly limited either, and they may be mixed with each other in a substantially solvent-free or completely solvent-free state, or may be mixed with an appropriate solvent.

It is preferable that the solvent used as necessary when mixing these is a solvent that transmits them completely or partially when irradiated with light having a wavelength of 200 to 450 nm. The choice of this solvent can be determined by known solubility data, spectral data and / or simple preliminary experiments.

For the photopolymerization in the method of the present invention, a known and commonly used light irradiation device can be used. For example, a general photopolymerization device such as a quartz reactor, or a photosensitive device using lamps of various shapes can be used. For example, an irradiation device for a conductive resin can be used.

The light source used in the method of the present invention is preferably an ordinary light source that emits light having a wavelength of 200 to 450 nm. Examples of preferable light sources include, for example, commonly used lamps for sterilization and sterilization, UV-fluorescent tubes, high-pressure or low-pressure mercury lamps, super-active fluorescent lamps, xenon lamps, metal halide lamps, carbon lamps, lasers (eg, gas lasers) and the like. .

In the method of the present invention, the time for irradiating the mixture of the polymer photoinitiator and the fluorine-containing vinyl monomer (II) with light having a wavelength of from 200 to 450 nm is not particularly limited. Until the monomer (II) is polymerized at the terminal of the agent, a polymer portion or an oligomer portion is formed by the vinyl monomer (II).

The photopolymerization reaction time is not particularly limited, and is usually from several seconds to several hours. However, the polymer initiator to be used and the vinyl monomer (II) or other monomer to be copolymerized therewith are used. It depends on the combination with the monomer and may be determined as appropriate. The optimum irradiation time for the reaction intermediate used can be easily confirmed by conducting a preliminary experiment.

A particularly preferred embodiment of the method of the present invention is
One polymer segment of the block copolymer (this is a compound (I), ie, a segment derived from a polymer initiator) is efficiently synthesized by thermal polymerization with few synthetic restrictions, and then the polymer segment is included from the polymer segment. Photopolymerizing a fluorovinyl monomer (II) as an essential monomer,
The other segment (a polymer segment derived from the monomer (II) or a copolymer segment of the monomer (II) and a copolymerizable monomer) is formed, and the fluorine-containing (co) polymer segment is formed. This is a method of obtaining a fluorinated block copolymer having the same.

The fluorinated block copolymer obtained by the method of the present invention is separated from the reaction product by a known technique. For example, in the case of a solvent-containing system, a precipitation method or an evaporation method can be used. If the mixture consisting of the polymer photoinitiator and the vinyl monomer (II) before polymerization is almost completely converted into a block copolymer without any solvent, this step can of course be omitted. Further, for example, separation can be performed by extraction, immersion, precipitation, chromatography, or the like.

At any stage of the photopolymerization step of the present invention, additives may be added to a system comprising a mixture of a polymeric photoinitiator and a vinyl monomer (II). However, it is preferable that the additive does not extremely delay or inhibit the block copolymerization reaction of the two main compounds.

Examples of these additives include polymer or oligomer binders generally used in the field of photosensitive recording materials, thermal polymerization inhibitors, dyes, pigments (dyes), photochromics, additives for improving the relief structure, Examples thereof include a crosslinking auxiliary, an antioxidant, an antiozonant, a filler, a flux, and a release agent.

The use of the fluorinated block copolymer obtained by the method of the present invention is not particularly limited. For example, various materials such as metal, plastic, glass, wood and fiber, and surface modifiers for paints and synthetic leathers and the like. Water and oil repellents;
Surfactants; compatibilizers; elastomers; films; That is, the fluorinated block copolymer obtained by the method of the present invention can be used alone or by adding it to other materials depending on the application.

The advantages of the method of the present invention are that, first, a block copolymer excellent in weather resistance and stain resistance can be synthesized, and second, various combinations of block copolymers can be synthesized. That is. The method according to the invention has many advantages. This can be said not only for the method but also for the obtained fluorine-containing copolymer. The method of the present invention is applicable in many fields.

[0074]

EXAMPLES Next, Examples, Comparative Examples and Test Examples will be given in order to explain the present invention in more detail. Example 1 26.84 g of dipropylene glycol, 35.32 g of hexamethylene diisocyanate, 53.50 g of methyl ethyl ketone and 53.50 g of dibutyltin dilaurate 1 were placed in a glass flask equipped with a stirrer, a condenser and a thermometer.
0 mg was charged and reacted at a reflux temperature under a nitrogen gas atmosphere for 90 minutes. Subsequently, 3.84 g of a photoinitiator Darocure 2959 manufactured by Ciba-Geigy was added, and the mixture was further reacted at a reflux temperature for 2 hours. The molecular weight of this polymer in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) was Mn = 16,900. It was also confirmed that all of Darocur 2959 had reacted with the end of the polyurethane chain. This polyurethane-type polymer photoinitiator is referred to as polymer photoinitiator 1. The polymer photoinitiator 1 was used for the next reaction without purification in a methyl ethyl ketone solution having a solid content of 42% by weight.

The Darocure 2959 has the following structure.

[0076]

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Next, 38.10 g of the polymer photoinitiator 1 solution, 25.00 g of methyl ethyl ketone, were placed in a 250 ml Pyrex glass flat bottom flask equipped with a stirrer.
4.00 g of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate was charged, and the mixture was stirred at room temperature and under a nitrogen atmosphere while a high-pressure mercury lamp with an output of 230 W (Uvahand 250 manufactured by Dr. Heenle, distance 10).
UV density in 35 cm / cm ² ) from 10 cm at a distance of 10 cm
Irradiated with ultraviolet rays for 1 minute to obtain a solution of the desired fluorinated block copolymer (which has a polyurethane segment and a fluoroacrylate polymer segment in a block shape) in methyl ethyl ketone (solid content: 30% by weight).

Note that 1H, 1 was examined using proton NMR.
The conversion of H, 2H, 2H-heptadecafluorodecyl acrylate was 100%, and the result of GPC measurement was Mn
= 18,200. Further, the obtained fluorinated block copolymer solution was spread in a thin film on a polypropylene plate, and the solvent was distilled off at 40 ° C. under reduced pressure to separate the fluorinated block copolymer. 1,1,2 of the separated solid
-In the extraction experiment with trichlorotrifluoroethane,
The extractable content was very low at 0.2%, and it was found that most of the polymerized fluorine-containing vinyl monomer was taken into the polymer photoinitiator to form a block copolymer.

Example 2 Polypropylene glycol (molecular weight: 425) 2 was placed in a glass flask equipped with a stirrer, a condenser, and a thermometer.
6.26 g and 2,4-toluylene diisocyanate 1
3.93 g, 26.48 g of acetonitrile and 40 mg of dibutyltin dilaurate were charged under nitrogen atmosphere.
The reaction was performed at 5 ° C. for 90 minutes. Subsequently, 7.03 g of the above-mentioned photoinitiator Darocure 2959 was added, and the mixture was further added at 50 ° C.
For 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure.
A pale yellow viscous liquid polyurethane-type polymer photoinitiator was obtained. GPC measurement result of this polymer showed that Mn = 3,40.
It was 0. This polyurethane-type polymer photoinitiator is referred to as polymer photoinitiator 2.

Next, in a pressure-resistant sealed tube made of Pyrex glass,
10 g of a polymer photoinitiator, 2.25 g of methyl ethyl ketone, 10 g of ethyl vinyl ether, 10 g of vinyl acetate and 20 g of liquefied and collected chlorotrifluoroethylene were charged at room temperature at a distance of 10 cm from the high pressure mercury lamp described above. Irradiated with ultraviolet rays for 8 hours to obtain a desired fluorinated block copolymer (which has a polyurethane segment and a fluoroolefin copolymer segment in a block shape). The result of the GPC measurement was M
n = 24,000.

Example 3 A glass flask equipped with a stirrer was charged with 5.51 g of the above-mentioned photoinitiator Darocure 2959, 5.72 g of isophorone diisocyanate, 17.00 g of acetone and 5 mg of dibutyltin dilaurate. The reaction was carried out at 50 ° C. for 150 minutes in an atmosphere. Subsequently, 22.
80 g of polydimethylsiloxane having an aminopropyldimethyl group at the terminal of the polymer chain was added, and the mixture was further reacted at the same temperature for 1 hour. After completion of the reaction, the reaction solution is
It was poured into a mixed solvent of 5% by weight of water and 5% by weight of water, thoroughly stirred and purified. The precipitated polymer was dried under reduced pressure to obtain a pale yellow solid. The GPC measurement result of this polymer shows that Mn =
It was 10,000. This polydimethylsiloxane polymer photoinitiator is referred to as polymer photoinitiator 3.

Next, in a Pyrex glass sealed tube, 1 g
Polymer photoinitiator 3, 0.1 g of 2,2,2-trifluoroethyl methacrylate, 0.9 g of methyl methacrylate and 2.0 g of acetonitrile were charged and degassed and sealed. Ultraviolet fluorescent lamp (TL
8W / 08, Philips, UV irradiation intensity 0.0
Irradiated at a distance of 2.6 cm from 43 W / cm / lamp) for 1 hour to obtain a desired fluorinated block copolymer (which has a block structure with a polyorganosiloxane segment and a fluoroacrylate copolymer segment). . Note that GP
The result of the C measurement was Mn = 32,000.

Example 4 A glass flask equipped with a stirrer was charged with 5.00 g of the above photoinitiator Darocure 2959, 10.00 g of hexamethylene diisocyanate, 30.00 g of acetone and 8 mg of dibutyltin dilaurate,
The reaction was carried out at 50 ° C. for 90 minutes in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was poured into petroleum ether, and toluene /
It was purified once by reprecipitation in petroleum ether system. The product obtained by decantation was immediately treated with 30.00 g of polyester diol (Polylite ES5, Reichhold).
6) and 15.00 g of methyl ethyl ketone, and further reacted at 70 ° C. for 12 hours.

After completion of the reaction, the reaction solution was poured into a mixed solvent of 95% by weight of methanol and 5% by weight of water, and the mixture was thoroughly stirred and purified. The precipitated polymer was dried under reduced pressure to obtain a pale yellow solid. GPC measurement results of this polymer showed that Mn = 4.
700. This polyester-type polymer photoinitiator is referred to as polymer photoinitiator 4.

Next, in a Pyrex glass sealed tube, 1 g
Polymer photoinitiator 4, 0.1 g of 2,2,2-trifluoroethyl methacrylate, 0.9 g of methyl methacrylate and 2.0 g of acetonitrile, and after degassing and sealing, the above-mentioned 2 was obtained at room temperature. Irradiate at a distance of 2.6 cm from the ultraviolet fluorescent lamp for 1 hour to fluorinated block copolymer (this is a polyester segment,
And a fluoroacrylate polymerized segment in the form of a block. The result of the GPC measurement was Mn = 1.
It was 4,000.

Example 5 A glass flask equipped with a stirrer was charged with 5.00 g of the above photoinitiator Darocure 2959, 10.00 g of hexamethylene diisocyanate, 30.00 g of acetone and 8 mg of dibutyltin dilaurate.
The reaction was carried out at 50 ° C. for 90 minutes in a nitrogen atmosphere. After completion of the reaction, the reaction mixture was poured into petroleum ether, and toluene /
It was purified once by reprecipitation in petroleum ether system. The product obtained by decantation was immediately mixed with 30.00 g of polybutadiene diol and 15.00 g of methyl ethyl ketone, and further reacted at 70 ° C. for 12 hours.

After the completion of the reaction, the reaction solution was poured into methanol, stirred well, and purified. The precipitated polymer was dried under reduced pressure to obtain a pale yellow solid. The result of GPC measurement of this polymer was Mn = 9,000. This polybutadiene-type polymer photoinitiator is referred to as polymer photoinitiator 5.

Next, in a Pyrex glass sealed tube, 1 g
Of polymer photoinitiator 5, 0.1 g of 2,2,2-trifluoroethyl methacrylate, 0.9 g of methyl methacrylate and 8.0 g of acetonitrile, and after degassing and sealing, the above-mentioned 2 was obtained at room temperature. Irradiation was performed at a distance of 2.6 cm from the ultraviolet fluorescent lamp for 20 minutes to obtain a desired fluorinated block copolymer (having a polybutadiene segment and a fluoroacrylate copolymer segment in a block shape). The result of the GPC measurement was Mn
= 18,000.

Example 6 A glass flask equipped with a stirrer, a dropping device and a thermometer was charged with 5.50 g of benzoin, 2.01 g of pyridine and 100 ml of chloroform.
4.04 g of 4,4'-azobis- prepared in advance in C
A mixture of 4-cyanovaleric chloride and 50 ml of chloroform was added dropwise, and the mixture was further reacted at 0 ° C. for 5 hours and at room temperature for 12 hours.
4'-azobis- (4-cyanopentanoyl) -bis-
Benzoin was synthesized. Subsequently, 0.092 g of the synthesized 4,4′-azobis- was placed in a Pyrex glass sealed tube.
(4-Cyanopentanoyl) -bis-benzoin and 4.70 g of methyl methacrylate were charged and polymerized at 80 ° C. for 45 minutes. After completion of the reaction, the reaction mixture was poured into methanol, and purified by reprecipitation twice with methylene chloride / methanol to obtain a desired polymer photoinitiator.

The GPC measurement result of this polymer showed that Mn = 1.
It was 50,000. This polymethyl methacrylate type polymer photoinitiator is referred to as polymer photoinitiator 6.

Next, put 1 g in a Pyrex glass sealed tube.
Polymer photoinitiator 6, 0.3 g of 1H, 1H, 2H, 2
H-heptadecafluorodecyl methacrylate, 2.7
g of styrene and 3.0 g of toluene, and after degassing and sealing, irradiate at room temperature for 10 hours at a distance of 10 cm from the above two ultraviolet fluorescent lamps for 8 hours to obtain the desired fluorinated block copolymer (this is Having a polymethyl methacrylate segment and a fluoroacrylate copolymer segment in a block shape). The result of the GPC measurement was Mn = 170,000.

Example 7 6.52 g of α-methylol benzoin methyl ether, 2.01 g of pyridine and 100 ml of chloroform were charged into a glass flask equipped with a stirrer, a dropping device, and a thermometer. A mixture of 4.04 g of 4,4'-azobis-4-cyanovaleric acid chloride and 50 ml of chloroform prepared in advance in C was added dropwise, and the mixture was further reacted at 0 ° C. for 5 hours and at room temperature for 12 hours. And purified by recrystallization in 4,4'-azobis- (4
-Cyanopentanoyl) -bis- (α-methylol benzoin methyl ether) was synthesized. Subsequently, 0.092 g of the synthesized 4,4 ′ was placed in a Pyrex glass sealed tube.
-Azobis- (4-cyanopentanoyl) -bis- (α
-Methylol benzoin methyl ether) and 4.7
0 g of methyl methacrylate was charged, and was
Polymerization was performed for minutes.

After the completion of the reaction, the reaction mixture was poured into methanol, and purified by reprecipitation twice with methylene chloride / methanol to obtain a desired polymer photoinitiator. G of this polymer
The PC measurement result was Mn = 130,000. This polymethyl methacrylate type polymer photoinitiator is referred to as polymer photoinitiator 7.

Next, in a Pyrex glass sealed tube, 1 g
Polymer photoinitiator 7, 0.3 g of 1H, 1H, 2H, 2
H-heptadecafluorodecyl methacrylate, 2.7
g of styrene and 3.0 g of toluene, and after degassing and sealing, irradiate at room temperature for 10 hours at a distance of 10 cm from the above two ultraviolet fluorescent lamps for 8 hours to obtain the desired fluorinated block copolymer (this is Having a polymethyl methacrylate segment and a fluoroacrylate copolymer segment in a block shape). The result of the GPC measurement was Mn = 150,000.

Comparative Example 1 26.84 g of dipropylene glycol, 35.32 g of hexamethylene diisocyanate, 53.50 g of methyl ethyl ketone and 10 m of dibutyltin dilaurate were placed in a glass flask equipped with a stirrer, a condenser and a thermometer.
g, and reacted at reflux temperature for 90 minutes under a nitrogen gas atmosphere. The mixture was cooled to room temperature, and 1.68 g of an azo polymerization initiator VF-077 manufactured by Wako Pure Chemical Industries, Ltd. was added.
Stirring was continued at 5 ° C. However, unreacted VF-077 was also observed by GPC in the reaction mixture after 3 days.

This is because the molecular weight of the polyurethane chain before the chain extension with VF-077 is already 16,000 in number average molecular weight.
Due to the above-mentioned high value, heating is originally required for accelerating the reaction, but the heating is not possible due to protection of the azo functional group.

Since this unreacted VF-077 is not preferable for the subsequent block copolymer synthesis, it is washed with ion-exchanged water, filtered, and dried under reduced pressure at 25 ° C. in order to remove it. Needs arise. Through the above post-treatment process, the desired azo group-containing polyurethane type polymer initiator was obtained. The GPC measurement result of this polymer is M
n = 27,000. This azo group-containing polyurethane polymer initiator is referred to as an azo polymer initiator.

Next, in a 100 ml Pyrex glass round bottom flask equipped with a stirrer, a condenser and a thermometer,
16.00 g of azo type polymer initiator, 47.10 g of methyl ethyl ketone, 4.00 g of 1H, 1H, 2H, 2H
-Heptadecafluorodecyl acrylate was charged, and polymerized at 78 ° C for 24 hours in a nitrogen atmosphere to synthesize a fluorine-containing block copolymer for comparative purposes. However, the conversion of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, which was examined using proton NMR, remained unchanged after 15 hours of the reaction, and even after 24 hours, 20% of unreacted 1H, 1H, 2H, and 2H had remained. -Heptadecafluorodecyl acrylate was observed.

This is considered to be because the amount of the azo group corresponding to the true initiator portion in the azo type polymer initiator was insufficient for the above-mentioned reason. Thus, a fluorinated block copolymer containing an unreacted fluorinated vinyl monomer (which has a polyurethane segment and a fluoroacrylate polymerized segment in a block shape)
To give a methyl ethyl ketone solution.

Comparative Example 2 38.10 g of the polymer photoinitiator 1 solution described in Example 1, 25.00 g of methyl ethyl ketone, 4.00 g of methyl in a Pyrex glass 250 ml flat bottom flask equipped with a stirrer The methacrylate was charged, and the mixture was irradiated with ultraviolet light at a distance of 10 cm from the above-described high-pressure mercury lamp for 10 minutes while stirring at room temperature and under a nitrogen atmosphere, and a polyurethane segment derived from the initiator and a polymethyl derived from the monomer were irradiated. A methyl ethyl ketone solution (solid content 30% by weight) of a fluorine-free block copolymer having a methacrylate segment in a block shape was obtained.
As a result of GPC measurement, Mn was 19,000.

Test Example 1 A polyurethane synthesized in advance consisting of dipropylene glycol and hexamethylene diisocyanate (Mn = 2
3,000) and 100 parts by weight of a methyl ethyl ketone solution (solid content: 40% by weight) were mixed with 7 parts by weight of the methyl ethyl ketone solution of the fluorinated block copolymer obtained in Example 1. The solution was applied on a glass plate using a 0.254 mm applicator, and dried at 25 ° C. for 168 hours to obtain a sample A-1.

Further, after this coating film was immersed in ethanol for 5 minutes, taken out, and further dried for 168 hours, it is referred to as Sample A-2. At the center of this sample plate, black ink for a fountain pen was dropped with a spoid until it spread to a diameter of about 15 mm. The surface of the liquid was covered with a watch glass and left at room temperature for 24 hours. did. Table 1 shows the results.

Test Example 2 100 parts by weight of the polyurethane methyl ethyl ketone solution described in Test Example 1 and 7 parts by weight of the methyl ethyl ketone solution of the fluorine-containing block copolymer obtained in Comparative Example 1 were mixed. The solution was applied, dried, immersed and dried by the method described in Test Example 1 to obtain Sample B-1 and Sample B-2, respectively. This sample plate was subjected to the same treatment as in Test Example 1 and evaluated. Table 1 shows the results.

Test Example 3 100 parts by weight of the polyurethane methyl ethyl ketone solution described in Test Example 1 and 7 parts by weight of the methyl ethyl ketone solution of the block copolymer containing a polymethyl methacrylate segment obtained in Comparative Example 2 were mixed. . This solution was applied, dried, immersed and dried by the method described in Test Example 1 to obtain Sample C-1 and Sample C-, respectively.
Let it be 2. This sample plate was subjected to the same treatment as in Test Example 1 and evaluated. Table 1 shows the results.

[0105]

[Table 1]

As can be seen from Table 1, it is clear that the fluorinated block copolymer obtained by the production method of the present invention has excellent antifouling property even under severe conditions. When the same evaluation as in Test Example 1 was performed using each of the fluorine-containing block copolymers obtained in Examples 2 to 7, even in each of the samples prepared under the condition of ethanol immersion as in Test Example 1, In each case, an evaluation of “◎” was obtained.

Further, each of the block copolymer films of Examples 1 to 7 was not colored or peeled off by the weather resistance test. In comparison, it had extremely excellent performance.

As is clear from the comparison between the synthesis experiments of Example 1 and Comparative Example 1 and the results shown in Table 1, the method for synthesizing the fluorinated block copolymer of the present invention has limitations on the reaction conditions during the synthesis. It is known that the degree of freedom of combination of polymer segments of a fluorine-containing block copolymer which can be synthesized is extremely low. It is also known that the synthesized fluorinated block copolymer has high properties such as excellent stain resistance and can be imparted to other resins.

[0109]

According to the present invention, a polymer compound having photopolymerization initiation ability and a fluorine-containing vinyl monomer are photopolymerized to block the polymer compound segment and the fluorine-containing vinyl monomer polymer segment. Since a fluorine-containing block copolymer having a shape is obtained, there is no need to precisely control polymerization conditions, and a step of removing a large amount of unreacted monomer remaining when obtaining a block copolymer by thermal polymerization is performed. It is unnecessary and has a particularly remarkable effect that a block copolymer film having excellent antifouling resistance and weather resistance can be obtained.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 293/00 C08F 2/50

Claims (3)

(57) [Claims] 1. A method for irradiating one or both ends of a polymer chain with a compound having a terminal functional group capable of initiating photopolymerization by irradiating light having a wavelength of 200 to 450 nm. A process for producing a fluorine-containing block copolymer, comprising photopolymerizing the monomer (II) as an essential monomer. 2. The method according to claim 1, wherein the terminal functional group of the compound (I) is a terminal functional group having the following structure. Embedded image 3. The process according to claim 1, wherein the compound (I) has at least one terminal functional group selected from the following terminal functional groups. Embedded image (Wherein, R1 and R2 are hydrogen atoms and carbon atoms of 1 to 12)
A substituted or unsubstituted phenyl group, a hydroxymethyl group or an alkoxymethyl group having 1 to 4 carbon atoms, which may be the same or different. R3
Represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a hydroxymethyl group,
To 4 alkoxymethyl groups or an alkanoyl group having 1 to 12 carbon atoms. ) (In the formula, R4 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms or an alkoxymethyl group having 1 to 4 carbon atoms. R5 and R6 each represent a substituted or unsubstituted phenyl group. And n may be 0
To an integer from 4 to 4. ) (Wherein, R7 and R8 are hydrogen atoms and have 1 to 12 carbon atoms)
Or an alkanoyl group having 1 to 12 carbon atoms, which may be the same or different. R9 represents a substituted or unsubstituted phenyl group. )