JPH10130185A - Polyfunctional vinyl ether, polymerizable composition, hardened material and production of polyfunctional vinyl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound being slightly effected with oxygen, capable of realizing low irritation to skin and low odor and useful in the fields of ink, coating materials and adhesives, etc., by introducing a vinyl ether group into (di)pentaserythritol. SOLUTION: This compound is expressed by formula I [(n) is 1 or 2; X is H or a group of formula II (m) is 0-2} in which 50-95% of (2n+2) pieces of X are the groups of the formula II] and is obtained by reacting a compound of formula III (1) is same as (n)} with a compound of formula IV Y is a halogen; (K) is same as (m)} in the presence of an inorganic fine powder, e.g. sodium sulfate anhydride, calcium carbonate anhydride or zeolite and basic compound such as sodium hydroxide, triethylamine or alkali metal alcoholate.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a novel polyfunctional vinyl ether, a polymerizable composition, a cured product, and a method for producing the polyfunctional vinyl ether.

[0002]

2. Description of the Related Art At present, polymerizable compositions such as ultraviolet curable resins and electron beam curable resins are mainly used in many fields such as inks, paints, adhesives, resists and plate-making materials. As the main agent, acrylic monomers and polyfunctional acrylates are most common.

[0003]

However, acrylic monomers have problems associated with skin irritation, odor, and the action of inhibiting polymerization by oxygen. Therefore, recently, vinyl ethers having low skin irritation, low odor, and little influence of oxygen have attracted attention. Further, since vinyl ether shows a high curing rate in a cationic polymerization system, further superiority can be expected as compared with acrylic monomers.

[0004]

Means for Solving the Problems The present inventors have found that they have low skin irritation represented by the following formula (A) and are extremely useful in various fields, and have completed the present invention.
That is, the present invention provides:

[0005]

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(In the formula (A), n represents an integer of 1 to 2;
Represents H or the formula (1), and 50 to 95% of 2n + 2 Xs represent the formula (1)

[0007]

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In the presence of a polyfunctional vinyl ether represented by the formula (1), m represents an integer of 0 to 2, (2) a basic compound and an inorganic fine powder,

[0009]

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(In the formula (2), 1 represents an integer of 1 to 2.)
And a compound represented by the formula (3)

[0011]

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(In the formula (3), Y is a halogen atom, k is 0 to 0)
Represents an integer of 2. A) producing a polyfunctional vinyl ether represented by the formula (A), and (3) polymerizing a polyfunctional vinyl ether containing the polyfunctional vinyl ether represented by the formula (A). The composition, (4) the above (3)
And a cured product obtained by curing the polymerizable composition described in the above item.

[0013]

DETAILED DESCRIPTION OF THE INVENTION As a general method for synthesizing a compound represented by the formula (A), a compound represented by the formula (2) and a haloaliphatic vinyl ether compound represented by the formula (3) are used. By reacting in the presence of a basic compound.

Specific examples of the compound of the formula (2) that can be used include pentaerythritol, dipentaerythritol,
And mixtures thereof. The compound of the formula (2) is usually hardly soluble in solvents other than water, and the reaction usually proceeds in a heterogeneous system. Further, the compound of the formula (2) has poor dispersibility in most organic solvents, and solids aggregate in the reaction system. At this time, the coexistence of the inorganic fine powder in the reaction system is preferable because the dispersibility of the solid component is improved, the reaction rate and the yield are improved.

The inorganic fine powder is not particularly limited as long as it is insoluble or hardly soluble in the reaction system. Specific examples of the inorganic fine powder that can be used include sulfates, carbonates, phosphates, inorganic salts such as titanates, alumina, aluminum hydroxide, iron oxide, titanium oxide, and metal oxides such as Hydroxides, zeolites, mordenites,
Montmorillonite, hydroxyapatite, granulated blast furnace slag, silica gel, metallosilicate, shirasu, fine sand,
Fine sand, activated carbon, carbon black and the like. Among these inorganic fine powders, those having a dehydrating effect, such as anhydrous sodium sulfate, anhydrous calcium carbonate and zeolite, are preferred. These inorganic fine powders, not only alone,
It is also possible to use a mixture of two or more types. The amount of the inorganic fine powder to be used is such that the use ratio of the inorganic fine powder to the compound of the formula (2) is usually 1:99 to 80:20, preferably 30:80.
70-60: 40 (inorganic fine powder: compound of formula (2))
The particle size is usually 100 nm to 1 mm, preferably 1 μm to 300 μm.

Specific examples of the compound of the formula (3) that can be used include vinyl bromide, chloroethyl vinyl ether, bromoethyl vinyl ether, chloroethoxyethyl vinyl ether and the like. The amount of the compound of the formula (3) to be used is generally 0.1 mol or more, preferably 0.5 mol to 2 mol, per 1 mol equivalent of the OH group of the compound of the formula (2).

Specific examples of the basic compound that can be used include:
Examples thereof include alkali metal compounds such as sodium hydroxide, potassium hydroxide, and sodium hydride; amines such as triethylamine and pyridine; alkali metal alcoholates such as sodium methylate; and alkali metals such as sodium metal. Is usually 0.5 to 1 with respect to 1.0 molar equivalent of the OH group of the compound of the formula (2).
0 mol, preferably 1.0 to 3.0 mol. At this time, tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate, tetraphenylammonium chloride, trioctylmethylammonium chloride, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, 18-crown-6, polyethylene The reaction is further accelerated when a phase transfer catalyst such as glycol is used in combination. The amount of the phase transfer catalyst to be used is generally 0.1 to 2 with respect to 1.0 molar equivalent of the OH group of the compound of the formula (2).
0 mol%, preferably 0.5 to 10 mol%.

The reaction is carried out in an inert solvent such as dimethylsulfoxide, dimethylsulfone, dimethylformamide,
Aprotic polar solvents such as N-methylpyrrolidone and N, N-dimethylimidazolidone; non-polar solvents such as toluene, hexane and heptane; tetrahydrofuran, diglyme, dioxane, trioxane and the like, or a mixed solvent thereof. Is also good. The amount of these solvents to be used is generally 0 to 5 relative to 0.1 mol of the compound of the formula (2).
00 ml, preferably 50-200 ml. The reaction temperature is usually 30 to 150 ° C, preferably 60 to 110 ° C,
The reaction time is generally 5 to 48 hours, preferably 10 to 24 hours. Further, the reaction can be allowed to proceed while removing the water generated by the reaction outside the reaction system.

After completion of the reaction, the reaction mixture is cooled to room temperature and filtered. The filtrate is then methyl ethyl ketone,
After washing with diethyl ether, hexane or the like, the washing solution is combined with the filtrate, and the organic layer is washed several times with water to remove unreacted compound of the formula (2), by-product inorganic salts and the like. Then, after drying the organic layer with a drying agent such as anhydrous sodium sulfate,
The target product (the polyfunctional vinyl ether of the present invention represented by the formula (A)) can be obtained by removing the solvent under reduced pressure.

Next, the polymerizable composition of the present invention will be described. The polymerizable composition of the present invention is prepared by mixing a predetermined amount of the polyfunctional vinyl ether of the present invention, a polymerization initiator, and various other polymerizable compounds, dyes, pigments, plasticizers, inorganic fillers, solvents, and the like as necessary. Can be obtained. The polymerization initiator is not particularly limited as long as it can cause radical polymerization or ionic (cation) polymerization, such as a thermal polymerization initiator or a photopolymerization initiator.

Specific examples of the thermal polymerization initiator that can be used include:
Benzoyl peroxide, acetyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile and the like. .

Specific examples of the photoradical polymerization initiator that can be used include 2,4-diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate,
-Dimethylaminoethyl benzoate and the like.

Specific examples of the cationic photopolymerization initiator that can be used include JP-B-53-32831 and JP-B-52-14.
No. 277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-1
No. 4279, JP-B-52-25686, JP-B-61-
34752, JP-A-54-53181, JP-A-54-53181
-95686, JP-B-61-36530, JP-B-5
9-19581, JP-B-63-65688, JP-A-55-164204, JP-B-60-30690, JP-B-63-36332, JP-B1-39423, JP-B2-10171, JP-B2-10171 5-15721, Japanese Patent Publication No. 4-62310, Japanese Patent Publication No. 62-57653, Japanese Patent Publication No. 3-12081, Japanese Patent Publication No. 3-12082, Japanese Patent Publication No. 3-16361, Japanese Patent Publication No. 63-12092, Japanese Patent Publication No. Sho 63 -12093, JP-B-63-12095, JP-B-63-12094, JP-B-2-37924, JP-B-2-35764, JP-B-4-13374, JP-B-4-75908, and JP-B-4- 73428 No. 5
3-32831, JP-A-2-150848, JP-A-2-296514, U.S. Pat. No. 4,069,055
No. 4,069,056, U.S. Pat.
703,296 and the like,
Examples thereof include diazonium salts, ammonium salts, phosphonium salts, iodonium salts, arsonium salts, and iron / arene complexes.

These polymerization initiators are usually used in an amount of 0.01 to 50% by weight, preferably 0.1% by weight, based on the compound of the formula (A).
-20% by weight, and may be mixed with the compound of the formula (A) when obtaining the cured product of the present invention, or may be mixed in the polymerizable composition of the present invention.

The cured product of the present invention can be obtained by irradiating or heating ultraviolet light, an electron beam or a radiation with the aromatic polyfunctional vinyl ether of the present invention as it is, preferably as the polymerizable composition of the present invention.

[0026]

The polyfunctional vinyl ether of the present invention is used as a polymerizable composition having low skin irritation as a coating agent, an ink,
It is extremely useful in various fields such as paints, adhesives, resists, and plate-making materials, and is also useful as a precursor of a compound having another functional group different from vinyl ether.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, the hydroxyl equivalent and the vinyl equivalent are, in the obtained polyfunctional vinyl ether,
The ratio of X in formula (A) being a hydrogen atom and formula (1)
, Respectively.

Example 1 17 g of pentaerythritol and 10 parts of synthetic zeolite (particle size: about 150 μm) were placed in a 300 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device.
g, 0.5 g of tetrabutylammonium bromide and 100 ml of dimethyl sulfoxide, 30 g of powdered potassium hydroxide was added, and the mixture was stirred at 60 ° C. for 30 minutes. Then, 60 ml of 2-chloroethyl vinyl ether (0.59
Mol) is maintained at 60 to 9 while maintaining the temperature in the reactor at 80 ° C.
Drop in 0 minutes. The reaction is further completed at 75 to 80 ° C. for 24 hours.

The reaction is cooled to room temperature and filtered. The filtrate is washed three times with 30 ml of diethyl ether, the washing solution is combined with the filtrate, 100 g of water is added thereto, and the operation of separating the aqueous layer with a separating funnel and washing the organic layer with water is repeated three times. Next, anhydrous sodium sulfate is added to the organic layer, and the mixture is left overnight. After filtration, diethyl ether and excess chloroethyl vinyl ether were removed under reduced pressure to obtain 14 g of a polyfunctional vinyl ether of the present invention (hydroxyl equivalent 34%, vinyl equivalent 66%).

Example 2 17 g of pentaerythritol and anhydrous sodium sulfate (particle size: about 100 μm) were placed in a 300 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device.
10 g, 0.5 g of dibenzo-18-crown-6,
100 ml of heptane is charged and powdered potassium hydroxide 3
Add 0 g and stir at 60 ° C. for 30 minutes. Then, 60 ml of 2-chloroethyl vinyl ether was added to the reactor at a temperature of 8 mL.
While maintaining at 0 ° C, the solution is added dropwise for 60 to 90 minutes. 7 more
Continue the reaction at 5 to 80 ° C for 24 hours to complete.

The reaction is cooled to room temperature and filtered. The filtrate is washed three times with 30 ml of diethyl ether, the washing solution is combined with the filtrate, 100 g of water is added thereto, the aqueous layer is separated with a separating funnel, and the operation of washing the organic layer with water is repeated three times.
Next, anhydrous sodium sulfate is added to the organic layer, and the mixture is left overnight. After filtering this, diethyl ether, heptane,
Excess chloroethyl vinyl ether was removed under reduced pressure, and 18 g of the polyfunctional vinyl ether of the present invention (hydroxyl equivalent 13%,
(Vinyl group equivalent: 87%).

Example 3 17 g of pentaerythritol and granulated blast furnace slag (particle size: about 50 μm) were placed in a 300 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device.
g, 0.5 g of tetrabutylammonium bromide and 100 ml of hexane.
g and stirred at 40 ° C. for 30 minutes. Then, 60 ml of 2-chloroethyl vinyl ether is added dropwise over 60 to 90 minutes under reflux conditions in the reactor. The reaction is further continued for 48 hours under reflux conditions to complete the reaction.

The reaction is cooled to room temperature and filtered. The filtrate is washed three times with 50 ml of diethyl ether, the washing solution is combined with the filtrate, 100 g of water is added thereto, the aqueous layer is separated with a separating funnel, and the operation of washing the organic layer with water is repeated three times. Next, anhydrous sodium sulfate is added to the organic layer, and the mixture is left overnight. After filtration, diethyl ether, hexane and excess chloroethyl vinyl ether were removed under reduced pressure to obtain 16 g of a polyfunctional vinyl ether of the present invention (hydroxyl equivalent 24%, vinyl equivalent 76%).

Example 4 17 g of pentaerythritol and 0.5 g of tetrabutylammonium bromide were placed in a 500 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device and a stirring device.
g and 100 ml of heptane, 30 g of powdered potassium hydroxide was added, and the mixture was stirred at 60 ° C. for 30 minutes. Then 2
60 ml of chloroethyl vinyl ether are added dropwise over a period of 60 to 90 minutes, keeping the temperature in the reactor at 80 ° C. The reaction is further completed at 75 to 80 ° C. for 24 hours.

The reaction is cooled to room temperature and decanted. 100 ml of diethyl ether and 100 g of water are added to the obtained supernatant, and the target compound is extracted into the organic layer. Separate the aqueous layer with a separating funnel and repeat the water washing of the organic layer three times.
Add anhydrous sodium sulfate to the organic layer and leave overnight. After filtration, diethyl ether, heptane and excess chloroethyl vinyl ether were removed under reduced pressure to obtain 7.8 g of a multifunctional vinyl ether of the present invention (hydroxyl equivalent 48%, vinyl equivalent 52%).

Claims (4)

[Claims] (1) Formula (A) (In the formula (A), n represents an integer of 1 to 2, X represents H or the formula (1), and 50 to 95% of 2n + 2 Xs
Is the formula (1) (Wherein m in the formula (1) represents an integer of 0 to 2).) 2. A compound of the formula (2) in the presence of a basic compound and an inorganic fine powder. (Wherein l in the formula (2) represents an integer of 1 to 2), and a compound represented by the formula (3): (Wherein Y represents a halogen atom and k represents an integer of 0 to 2 in the formula (3)), wherein the compound represented by the formula (A) is reacted with a compound represented by the formula (A). Manufacturing method. 3. A polymerizable composition containing a polyfunctional vinyl ether represented by the formula (A). 4. A cured product obtained by curing the polymerizable composition according to claim 3. [0001]