JP3791713B2 - Production method of polyfunctional vinyl ether - Google Patents

Description

【０００６】
（式（Ａ）中ｎは１〜２の整数を表し、ＸはＨまたは式（１）を表すが、２ｎ＋２個あるＸのうち５０〜９５％は式（１）
【０００７】
【化６】

【０００８】
（式（１）中ｍは０〜２の整数を表す。））で表される多官能ビニルエーテル、
（２）塩基性化合物および無機系微粉末の存在下で、式（２）
【０００９】
【化７】

【００１０】
（式（２）中ｌは１〜２の整数を表す。）で表される化合物と、式（３）
【００１１】
【化８】

【００１２】
（式（３）中Ｙはハロゲン原子、ｋは０〜２の整数を表す。）で表される化合物とを反応させることを特徴とする、前記式（Ａ）で表される多官能ビニルエーテルの製法、
（３）式（Ａ）で表される多官能ビニルエーテルを含有する重合性組成物、
（４）前記（３）項記載の重合性組成物を硬化してなる硬化物
に関する。
【００１３】
【発明の実施の形態】
式（Ａ）で表される化合物の一般的な合成法としては、式（２）で表される化合物と、式（３）で表されるハロ脂肪族ビニルエーテル化合物とを、塩基性化合物の存在下で反応させることによって得られる。
【００１４】
用い得る式（２）の化合物の具体例としては、ペンタエリスリトール、ジペンタエリスリトール、およびこれらの混合物などがある。式（２）の化合物は、通常水以外の溶媒に溶け難く、反応は通常、不均一系で進行する。また、式（２）の化合物はほとんどの有機溶媒に対して分散性も悪く、反応系内で固体同士が凝集する。このとき、無機系微粉末を反応系内に共存させることにより、固体分の分散性が向上し、反応速度および収率が向上し、好ましい。
【００１５】
無機系微粉末は、反応系に溶解しない、または溶解し難いものであれば特に限定されない。無機系微粉末の用い得る具体例としては、硫酸塩、炭酸塩、リン酸塩、チタン酸塩などの無機塩類や、アルミナ、水酸化アルミニウム、酸化鉄、チタン酸化物、などの金属酸化物および水酸化物類や、ゼオライト、モルデナイト、モンモリロナイト、ヒドロキシアパタイト、高炉水砕スラグ、シリカゲル、メタロシリケート、シラス、微砂、細砂、活性炭、カーボンブラックなどが挙げられる。これら無機系微粉末のうち無水硫酸ナトリウム、無水炭酸カルシウム、ゼオライトなど、脱水性効果を有するものが好ましい。これら無機系微粉末は、単独のみならず、２種類以上の混合使用も可能である。これら無機系微粉末の使用量は、無機系微粉末と式（２）の化合物との使用割合が通常１：９９〜８０：２０、好ましくは３０：７０〜６０：４０（無機系微粉末：式（２）の化合物）であり、その粒径は通常１００ｎｍ〜１ｍｍ、好ましくは１μｍ〜３００μｍである。
【００１６】
用い得る式（３）の化合物の具体例としては、臭化ビニル、クロルエチルビニルエーテル、ブロムエチルビニルエーテル、クロルエトキシエチルビニルエーテルなどが挙げられる。式（３）の化合物の使用量は、式（２）の化合物のＯＨ基１モル当量に対して通常０．１モル以上、好ましくは、０．５モル〜２モルである。
【００１７】
用い得る塩基性化合物の具体例としては、水酸化ナトリウム、水酸化カリウム、水素化ナトリウム、などのアルカリ金属化合物、トリエチルアミン、ピリジンなどのアミン、ナトリウムメチラートなどのアルカリ金属アルコラート、及び、金属ナトリウムなどのアルカリ金属などが挙げられ、その使用量は、式（２）の化合物のＯＨ基１．０モル当量に対して通常０．５〜１０モル、好ましくは１．０〜３．０モルである。またこの時、テトラブチルアンモニウムブロミド、テトラブチルアンモニウム硫酸水素塩、テトラフェニルアンモニウムクロリド、トリオクチルメチルアンモニウムクロリド、ジシクロヘキシル−１８−クラウン−６、ジベンゾ−１８−クラウン−６、１８−クラウン−６、ポリエチレングリコールなどの相間移動触媒を併用すれば反応はより促進される。相間移動触媒の使用量は、式（２）の化合物のＯＨ基１．０モル当量に対して通常０．１〜２０モル％、好ましくは０．５〜１０モル％である。
【００１８】
反応は、不活性溶媒、例えばジメチルスルホキシド、ジメチルスルホン、ジメチルホルムアミド、Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルイミダゾリドンのような非プロトン性極性溶媒、トルエン、ヘキサン、ヘプタン等の無極性溶媒、テトラヒドロフラン、ジグライム、ジオキサン、トリオキサン等、またはこれらの混合溶媒中で行なってもよい。これら溶媒の使用量は、式（２）の化合物０．１モルに対して、通常０〜５００ｍｌ、好ましくは５０〜２００ｍｌである。反応温度は通常３０〜１５０℃、好ましくは６０〜１１０℃、反応時間は通常５〜４８時間、好ましくは１０〜２４時間である。また反応で生成した水を反応系外に除去しながら反応を進行させることもできる。
【００１９】
反応終了後、反応混合液を室温まで冷却した後、濾過する。次いで濾過物をメチルエチルケトン、ジエチルエーテル、ヘキサンなどで洗浄し、洗浄液を濾液とあわせ更に有機層を数回水洗することで、未反応の式（２）の化合物、副生した無機塩等を除去する。次いで有機層を無水硫酸ナトリウムなどの乾燥剤で乾燥後、減圧下で溶剤を除去することにより目的物（式（Ａ）で表される本発明の多官能ビニルエーテル）を得ることができる。
【００２０】
次に本発明の重合性組成物につき説明する。
本発明の重合性組成物は、本発明の多官能ビニルエーテルと重合開始剤、及びその他必要に応じて種々の重合性化合物、染料、顔料、可塑剤、無機充填剤、溶剤などを所定量混合して得ることができる。重合開始剤としては、熱重合開始剤、光重合開始剤などのラジカル重合やイオン（カチオン）重合を起こしうるものであれば特に制限はない。
【００２１】
用いうる熱重合開始剤の具体例としては、過酸化ベンゾイル、過酸化アセチル、過酸化ラウロイル、ｔ−ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルバレロニトリル、アゾビスシクロヘキサンカルボニトリル等が挙げられる。
【００２２】
用いうる光ラジカル重合開始剤の具体例としては、２，４−ジエチルチオキサントン、ベンゾフェノン、４−ジメチルアミノイソアミルベンゾエート、４−ジメチルアミノエチルベンゾエート等が挙げられる。
【００２３】
用いうる光カチオン重合開始剤の具体例としては、特公昭５３−３２８３１号、特公昭５２−１４２７７号、特公昭５２−１４２７８号、特公昭５２−１４２７９号、特公昭５２−２５６８６号、特公昭６１−３４７５２号、特開昭５４−５３１８１号、特開昭５４−９５６８６号、特公昭６１−３６５３０号、特公昭５９−１９５８１号、特公昭６３−６５６８８号、特開昭５５−１６４２０４号、特公昭６０−３０６９０号、特公昭６３−３６３３２号、特公平１−３９４２３号、特公平２−１０１７１号、特公平５−１５７２１号、特公平４−６２３１０号、特公昭６２−５７６５３号、特公平３−１２０８１号、特公平３−１２０８２号、特公平３−１６３６１号、特公昭６３−１２０９２号、特公昭６３−１２０９３号、特公昭６３−１２０９５号、特公昭６３−１２０９４号、特公平２−３７９２４号、特公平２−３５７６４号、特公平４−１３３７４号、特公平４−７５９０８号、特公平４−７３４２８号、特公昭５３−３２８３１号、特開平２−１５０８４８号、特開平２−２９６５１４号、米国特許第４，０６９，０５５号、米国特許第４，０６９，０５６号、米国特許第３，７０３，２９６号等に記載されているスルホニウム塩、ジアゾニウム塩、アンモニウム塩、ホスホニウム塩、ヨードニウム塩、アルソニウム塩、鉄・アレーン錯体などが挙げられる。
【００２４】
これらの重合開始剤は式（Ａ）の化合物に対して、通常０．０１〜５０重量％、好ましくは０．１〜２０重量％使用され、本発明の硬化物を得る際に式（Ａ）の化合物と混合してもよいし、本発明の重合性組成物中に混合してもよい。
【００２５】
本発明の硬化物は、本発明の芳香族多官能ビニルエーテルをそのまま、好ましくは本発明の重合性組成物として、紫外線、電子線または放射線の照射もしくは加熱して得ることができる。
【００２６】
【発明の効果】
本発明の多官能ビニルエーテルは低皮膚刺激性の重合性組成物としてコーティング剤、インキ、塗料、接着剤、レジスト、製版材などの種々の分野において極めて有用であり、ビニルエーテルと異なる、他の官能基を有する化合物の前駆体としても有用である。
【００２７】
【実施例】
以下に本発明を実施例によって本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。
尚、実施例において水酸基当量及びビニル基当量は、得られた多官能ビニルエーテルにおいて、式（Ａ）におけるＸが水素原子である割合及び式（１）である割合をそれぞれ表す。
【００２８】
実施例１
温度計、環流冷却器、滴下ロート、窒素導入装置、攪拌装置のついた３００ｍｌの反応器に、ペンタエリスリトール１７ｇ、合成ゼオライト（粒径約１５０μｍ）１０ｇ、テトラブチルアンモニウムブロミド０．５ｇと、ジメチルスルホキシド１００ｍｌを仕込み、粉末状水酸化カリウム３０ｇを加え、６０℃で３０分攪拌する。次いで２−クロルエチルビニルエーテル６０ｍｌ（０．５９モル）を、反応器内温度を８０℃に保ちながら６０〜９０分間で滴下する。さらに７５〜８０℃で２４時間反応を続けて完結させる。
【００２９】
反応液を室温に冷却し、濾過する。濾過物をジエチルエーテル３０ｍｌで３回洗浄し、洗浄液を濾液とあわせこれに水１００ｇを加えた後、分液ロートで水層を分別し有機層を水洗する操作を３回繰り返す。次いで、有機層に無水硫酸ナトリウムを加えて一夜放置する。これを濾過後、ジエチルエーテルと、過剰のクロルエチルビニルエーテルを減圧除去し、本発明の多官能ビニルエーテル１４ｇ（水酸基当量３４％、ビニル基当量６６％）を得た。
【００３０】
実施例２
温度計、環流冷却器、滴下ロート、窒素導入装置、攪拌装置のついた３００ｍｌの反応器に、ペンタエリスリトール１７ｇ、無水硫酸ナトリウム（粒径約１００μｍ）１０ｇ、ジベンゾ−１８−クラウン−６を０．５ｇと、ヘプタン１００ｍｌを仕込み、粉末状水酸化カリウム３０ｇを加え、６０℃で３０分攪拌する。次いで２−クロルエチルビニルエーテル６０ｍｌを、反応器内温度を８０℃に保ちながら６０〜９０分間で滴下する。さらに７５〜８０℃で２４時間反応を続けて完結させる。
【００３１】
反応液を室温に冷却し、濾過する。濾過物をジエチルエーテル３０ｍｌで３回洗浄し、洗浄液を濾液とあわせこれに水１００ｇを加えた後、分液ロートで水層を分別し、有機層を水洗する操作を３回繰り返す。次いで、有機層に無水硫酸ナトリウムを加えて一夜放置する。これを濾過後、ジエチルエーテル、ヘプタンと、過剰のクロルエチルビニルエーテルを減圧除去し、本発明の多官能ビニルエーテル１８ｇ（水酸基当量１３％、ビニル基当量８７％）を得た。
【００３２】
実施例３
温度計、環流冷却器、滴下ロート、窒素導入装置、攪拌装置のついた３００ｍｌの反応器に、ペンタエリスリトール１７ｇ、高炉水砕スラグ（粒径約５０μm）１０ｇ、テトラブチルアンモニウムブロミド０．５ｇと、ヘキサン１００ｍｌを仕込み、粉末状水酸化カリウム３０ｇを加え、４０℃で３０分攪拌する。次いで２−クロルエチルビニルエーテル６０ｍｌを、反応器内環流条件下６０〜９０分間で滴下する。さらに環流条件下４８時間反応を続けて完結させる。
【００３３】
反応液を室温に冷却し、濾過する。濾過物をジエチルエーテル５０ｍｌで３回洗浄し、洗浄液を濾液とあわせこれに水１００ｇを加た後、分液ロートで水層を分別し有機層を水洗する操作を３回繰り返す。次いで、有機層に無水硫酸ナトリウムを加えて一夜放置する。これを濾過後、ジエチルエーテル、ヘキサンと、過剰のクロルエチルビニルエーテルを減圧除去し、本発明の多官能ビニルエーテル１６ｇ（水酸基当量２４％、ビニル基当量７６％）を得た。
【００３４】
実施例４
温度計、環流冷却器、滴下ロート、窒素導入装置、攪拌装置のついた５００ｍｌの反応器に、ペンタエリスリトール１７ｇ、テトラブチルアンモニウムブロミド０．５ｇと、ヘプタン１００ｍｌを仕込み、粉末状水酸化カリウム３０ｇを加え、６０℃で３０分攪拌する。次いで２−クロルエチルビニルエーテル６０ｍｌを、反応器内温度を８０℃に保ちながら６０〜９０分間で滴下する。さらに７５〜８０℃で２４時間反応を続けて完結させる。
【００３５】
反応液を室温に冷却し、デカントする。得られた上澄み液に、ジエチルエーテル１００ｍｌと、水１００ｇを加え、有機層へ目的化合物を抽出する。分液ロートで水層を分別し、有機層の水洗を３回繰り返し、有機層に無水硫酸ナトリウムを加えて一夜放置する。これを濾過後、ジエチルエーテル、ヘプタンと、過剰のクロルエチルビニルエーテルを減圧除去し、本発明の多感能ビニルエーテル７．８ｇ（水酸基当量４８％、ビニル基当量５２％）を得た。BACKGROUND 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]
[Prior art]
Currently, 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 platemaking materials. As the main agent, acrylic monomers and polyfunctional acrylates are the most common.
[0003]
[Problems to be solved by the invention]
However, acrylic monomers have various problems associated with skin irritation, odor and oxygen-induced polymerization inhibition. Accordingly, vinyl ethers have recently attracted attention because of their low skin irritation, low odor, and little influence of oxygen. Further, since vinyl ether exhibits a fast curing rate in a cationic polymerization system, it can be expected to have further superiority compared with an acrylic monomer.
[0004]
[Means for Solving the Problems]
The present inventors have found that the present invention has low skin irritation represented by the following formula (A) and is extremely useful in various fields. That is, the present invention
(1) Formula (A)
[0005]
[Chemical formula 5]

[0006]
(In formula (A), n represents an integer of 1 to 2, X represents H or formula (1), but 50 to 95% of 2n + 2 Xs are represented by formula (1).
[0007]
[Chemical 6]

[0008]
(In the formula (1), m represents an integer of 0 to 2))),
(2) In the presence of a basic compound and an inorganic fine powder, the formula (2)
[0009]
[Chemical 7]

[0010]
(Wherein l represents an integer of 1 to 2) and a compound represented by formula (3)
[0011]
[Chemical 8]

[0012]
(In formula (3), Y represents a halogen atom, k represents an integer of 0 to 2) and a compound represented by the above formula (A) is reacted. Manufacturing method,
(3) a polymerizable composition containing a polyfunctional vinyl ether represented by the formula (A);
(4) It relates to a cured product obtained by curing the polymerizable composition as described in (3) above.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
As a general method for synthesizing the compound represented by the formula (A), the compound represented by the formula (2) and the haloaliphatic vinyl ether compound represented by the formula (3) are used in the presence of a basic compound. Obtained by reacting under:
[0014]
Specific examples of compounds of formula (2) that can be used include pentaerythritol, dipentaerythritol, and mixtures thereof. The compound of formula (2) is usually hardly soluble in a solvent other than water, and the reaction usually proceeds in a heterogeneous system. Further, the compound of the formula (2) is poorly dispersible in most organic solvents, and solids aggregate in the reaction system. At this time, it is preferable to allow the inorganic fine powder to coexist in the reaction system because the dispersibility of the solid content is improved and the reaction rate and the yield are improved.
[0015]
The inorganic fine powder is not particularly limited as long as it is insoluble or difficult to dissolve in the reaction system. Specific examples of the inorganic fine powder that can be used include inorganic salts such as sulfates, carbonates, phosphates, titanates, metal oxides such as alumina, aluminum hydroxide, iron oxide, titanium oxide, and the like. Examples thereof include hydroxides, zeolite, mordenite, montmorillonite, hydroxyapatite, granulated blast furnace slag, silica gel, metallosilicate, shirasu, fine sand, fine sand, activated carbon, and carbon black. Among these inorganic fine powders, those having a dehydrating effect such as anhydrous sodium sulfate, anhydrous calcium carbonate, and zeolite are preferable. These inorganic fine powders can be used alone or in combination of two or more. The use amount of these inorganic fine powders is such that the use ratio of the inorganic fine powder and the compound of formula (2) is usually 1:99 to 80:20, preferably 30:70 to 60:40 (inorganic fine powder: The compound of formula (2)) has a particle size of usually 100 nm to 1 mm, preferably 1 μm to 300 μm.
[0016]
Specific examples of the compound of formula (3) that can be used include vinyl bromide, chloroethyl vinyl ether, bromoethyl vinyl ether, chloroethoxyethyl vinyl ether, and the like. The usage-amount of the compound of Formula (3) is 0.1 mol or more normally with respect to 1 mol equivalent of OH groups of the compound of Formula (2), Preferably, it is 0.5 mol-2 mol.
[0017]
Specific examples of basic compounds that can be used 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 sodium metal The amount used is usually 0.5 to 10 mol, preferably 1.0 to 3.0 mol, relative to 1.0 mol equivalent of the OH group of the compound of formula (2). . At this time, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, tetraphenylammonium chloride, trioctylmethylammonium chloride, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, 18-crown-6, polyethylene The reaction is further promoted if a phase transfer catalyst such as glycol is used in combination. The amount of the phase transfer catalyst used is usually 0.1 to 20 mol%, preferably 0.5 to 10 mol%, relative to 1.0 mol equivalent of the OH group of the compound of formula (2).
[0018]
The reaction is carried out by using an inert solvent such as dimethylsulfoxide, dimethylsulfone, dimethylformamide, aprotic polar solvent such as N-methylpyrrolidone, N, N-dimethylimidazolidone, nonpolar solvent such as toluene, hexane, heptane, tetrahydrofuran, etc. , Diglyme, dioxane, trioxane or the like, or a mixed solvent thereof. The amount of these solvents to be used is generally 0 to 500 ml, preferably 50 to 200 ml, relative to 0.1 mol of the compound of formula (2). The reaction temperature is usually 30 to 150 ° C., preferably 60 to 110 ° C., and the reaction time is usually 5 to 48 hours, preferably 10 to 24 hours. In addition, the reaction can be allowed to proceed while removing water produced by the reaction out of the reaction system.
[0019]
After completion of the reaction, the reaction mixture is cooled to room temperature and then filtered. Next, the filtrate is washed with methyl ethyl ketone, diethyl ether, hexane, etc., and the washing solution is combined with the filtrate, and the organic layer is washed with water several times to remove unreacted compound of formula (2), by-product inorganic salts, and the like. . Next, the organic layer is dried with a desiccant such as anhydrous sodium sulfate, and then the solvent is removed under reduced pressure to obtain the target product (polyfunctional vinyl ether of the present invention represented by the formula (A)).
[0020]
Next, the polymerizable composition of the present invention will be described.
The polymerizable composition of the present invention comprises 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, and solvents as required. Can be obtained. The polymerization initiator is not particularly limited as long as it can cause radical polymerization or ionic (cationic) polymerization such as a thermal polymerization initiator or a photopolymerization initiator.
[0021]
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-dimethyl. Examples include valeronitrile and azobiscyclohexanecarbonitrile.
[0022]
Specific examples of the photo radical polymerization initiator that can be used include 2,4-diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate, 4-dimethylaminoethylbenzoate, and the like.
[0023]
Specific examples of the cationic photopolymerization initiator that can be used include Japanese Patent Publication No. 53-32831, Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, Japanese Patent Publication No. 52-14279, Japanese Patent Publication No. 52-25686, and Japanese Patent Publication No. Sho. 61-34752, JP-A-54-53181, JP-A-54-95686, JP-B-61-36530, JP-B-59-19581, JP-B-63-65688, JP-A-55-164204, JP-B 60-30690, JP-B 63-36332, JP-B 1-33923, JP-B 2-10171, JP-B 5-15721, JP-B 4-62310, JP-B 62-57653, JP-B No. 3-12081, No. 3-12082, No. 3-16361, No. 63-12092, No. 63-12093, No. 6 -12095, JP-B 63-12094, JP-B 2-37924, JP-B 2-35764, JP-B 4-13374, JP-B 4-75908, JP-B 4-73428, JP-B 53- No. 32831, JP-A-2-150848, JP-A-2-296514, US Pat. No. 4,069,055, US Pat. No. 4,069,056, US Pat. No. 3,703,296, etc. Sulfonium salts, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, arsonium salts, iron / arene complexes, and the like.
[0024]
These polymerization initiators are usually used in an amount of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the compound of the formula (A). When the cured product of the present invention is obtained, the formula (A) It may be mixed with the above compound or may be mixed in the polymerizable composition of the present invention.
[0025]
The cured product of the present invention can be obtained by irradiating or heating the aromatic polyfunctional vinyl ether of the present invention as it is, preferably as a polymerizable composition of the present invention, with ultraviolet rays, electron beams or radiation.
[0026]
【The invention's effect】
The polyfunctional vinyl ether of the present invention is very useful as a low skin irritation polymerizable composition in various fields such as coating agents, inks, paints, adhesives, resists, plate-making materials, and other functional groups different from vinyl ether. It is also useful as a precursor of a compound having
[0027]
【Example】
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 group equivalent and the vinyl group equivalent represent the ratio in which X in the formula (A) is a hydrogen atom and the ratio in the formula (1), respectively, in the obtained polyfunctional vinyl ether.
[0028]
Example 1
A 300 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device, 17 g of pentaerythritol, 10 g of synthetic zeolite (particle size: about 150 μm), 0.5 g of tetrabutylammonium bromide, and dimethyl sulfoxide Charge 100 ml, add 30 g of powdered potassium hydroxide, and stir at 60 ° C. for 30 minutes. Subsequently, 60 ml (0.59 mol) of 2-chloroethyl vinyl ether is added dropwise over 60 to 90 minutes while maintaining the temperature in the reactor at 80 ° C. The reaction is further continued at 75-80 ° C. for 24 hours to complete the reaction.
[0029]
Cool the reaction to room temperature and filter. 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 then the aqueous layer is separated with a separatory funnel and the organic layer is washed with water three times. Then, anhydrous sodium sulfate is added to the organic layer and left overnight. After filtration, diethyl ether and excess chloroethyl vinyl ether were removed under reduced pressure to obtain 14 g (hydroxyl equivalent: 34%, vinyl group equivalent: 66%) of the present invention.
[0030]
Example 2
A 300 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device was charged with 0.1 g of pentaerythritol, 10 g of anhydrous sodium sulfate (particle size: about 100 μm), and dibenzo-18-crown-6. Charge 5 g and 100 ml of heptane, add 30 g of powdered potassium hydroxide, and stir at 60 ° C. for 30 minutes. Subsequently, 60 ml of 2-chloroethyl vinyl ether is dropped in 60 to 90 minutes while maintaining the temperature in the reactor at 80 ° C. The reaction is further continued at 75-80 ° C. for 24 hours to complete the reaction.
[0031]
Cool the reaction to room temperature and filter. The filtrate is washed 3 times with 30 ml of diethyl ether, the washing liquid is combined with the filtrate, 100 g of water is added thereto, the aqueous layer is separated with a separatory funnel, and the organic layer is washed with water 3 times. Then, anhydrous sodium sulfate is added to the organic layer and left overnight. After filtration, diethyl ether, heptane and excess chloroethyl vinyl ether were removed under reduced pressure to obtain 18 g of a polyfunctional vinyl ether of the present invention (hydroxyl equivalent: 13%, vinyl group equivalent: 87%).
[0032]
Example 3
In a 300 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device, 17 g of pentaerythritol, 10 g of granulated blast furnace slag (particle size of about 50 μm), 0.5 g of tetrabutylammonium bromide, Charge 100 ml of hexane, add 30 g of powdered potassium hydroxide, and stir at 40 ° C. for 30 minutes. Subsequently, 60 ml of 2-chloroethyl vinyl ether is added dropwise over 60 to 90 minutes under reflux conditions in the reactor. Further, the reaction is continued for 48 hours under reflux conditions to complete the reaction.
[0033]
Cool the reaction to room temperature and filter. The filtrate is washed 3 times with 50 ml of diethyl ether, the washing solution is combined with the filtrate, 100 g of water is added thereto, and then the aqueous layer is separated with a separatory funnel and the organic layer is washed with water 3 times. Then, anhydrous sodium sulfate is added to the organic layer and left overnight. After filtration, diethyl ether, hexane and excess chloroethyl vinyl ether were removed under reduced pressure to obtain 16 g of the polyfunctional vinyl ether of the present invention (hydroxyl equivalent 24%, vinyl group equivalent 76%).
[0034]
Example 4
A 500 ml reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device and a stirring device was charged with 17 g of pentaerythritol, 0.5 g of tetrabutylammonium bromide and 100 ml of heptane, and 30 g of powdered potassium hydroxide was added. In addition, the mixture is stirred at 60 ° C. for 30 minutes. Subsequently, 60 ml of 2-chloroethyl vinyl ether is dropped in 60 to 90 minutes while maintaining the temperature in the reactor at 80 ° C. The reaction is further continued at 75-80 ° C. for 24 hours to complete the reaction.
[0035]
Cool the reaction to room temperature and decant. To the obtained supernatant, 100 ml of diethyl ether and 100 g of water are added, and the target compound is extracted into the organic layer. The aqueous layer is separated with a separatory funnel, and the organic layer is washed with water three times. Anhydrous sodium sulfate is added to the organic layer and left overnight. After filtration, diethyl ether, heptane, and excess chloroethyl vinyl ether were removed under reduced pressure to obtain 7.8 g (hydroxyl group equivalent 48%, vinyl group equivalent 52%) of the present invention.

Claims (1)

In the presence of a basic compound and an inorganic fine powder, the formula (2)

(Wherein l represents an integer of 1 to 2) and a compound represented by formula (3)

(In formula (3), Y represents a halogen atom, k represents an integer of 0 to 2), and a polyfunctional vinyl ether represented by the following formula (A) is reacted. Manufacturing method.

(In formula (A), n represents an integer of 1 to 2 and X represents H or formula (1), but 50 to 95% of 2n + 2 Xs are represented by the following formula (1) (in formula (1) m represents an integer of 0 to 2.))

[0001]