JP2953545B2 - 1,9-nonanediol monovinyl ether and 1,9-nonanediol divinyl ether - Google Patents
1,9-nonanediol monovinyl ether and 1,9-nonanediol divinyl etherInfo
- Publication number
- JP2953545B2 JP2953545B2 JP14199692A JP14199692A JP2953545B2 JP 2953545 B2 JP2953545 B2 JP 2953545B2 JP 14199692 A JP14199692 A JP 14199692A JP 14199692 A JP14199692 A JP 14199692A JP 2953545 B2 JP2953545 B2 JP 2953545B2
- Authority
- JP
- Japan
- Prior art keywords
- nonanediol
- ether
- resin
- monovinyl
- monovinyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、例えば、紫外線硬化型
樹脂や電子線硬化型樹脂などの活性放射線硬化型樹脂に
用いられる低臭気、低揮発性および高希釈能を有する反
応性希釈剤および各種の樹脂改質剤や架橋剤として有用
な新規化合物である、1,9-ノナンジオールモノビニルエ
ーテル及び1,9-ノナンジオールジビニルエーテルに関す
る。BACKGROUND OF THE INVENTION The present invention relates to a reactive diluent having a low odor, a low volatility and a high diluting ability which is used for, for example, an active radiation-curable resin such as an ultraviolet-curable resin or an electron beam-curable resin. It relates to 1,9-nonanediol monovinyl ether and 1,9-nonanediol divinyl ether, which are novel compounds useful as various resin modifiers and crosslinking agents.
【０００２】[0002]
【従来の技術】従来、各種のポリアルキレンジオールの
ジビニルエーテルに関しては公知であり、例えば、JSDC
（Journal of the Society of Dyers and Colourists）
第81卷、第３号（1965年）、第108〜114頁には、ポリア
ルキレンジオールジビニルエーテルなどの各種のジビニ
ルエーテルによる綿の架橋に関して記載されている。2. Description of the Related Art Hitherto, divinyl ethers of various polyalkylene diols are known, for example, JSDC
(Journal of the Society of Dyers and Colorists)
Vol. 81, No. 3 (1965), pp. 108-114, describes the crosslinking of cotton with various divinyl ethers such as polyalkylene diol divinyl ether.
【０００３】しかしながら上記文献に具体的に開示され
ているポリアルキレンジオールジビニルエーテルは、1,
3−プロパンジオール及び1,5−ペンタンジオールのジビ
ニルエーテルのみであり、本発明の1,9-ノナンジオール
モノビニルエーテルに関してはもとより、1,9-ノナンジ
オールジニルエーテルに関しても何等記載されていな
い。[0003] However, the polyalkylenediol divinyl ethers specifically disclosed in the above-mentioned documents are 1,1
It is only divinyl ether of 3-propanediol and 1,5-pentanediol, and nothing is described about 1,9-nonanediol dinyl ether as well as 1,9-nonanediol monovinyl ether of the present invention.
【０００４】さらに本発明の1,9-ノナンジオールモノビ
ニルエーテル及び1,9-ノナンジオールジニルエーテルに
関しては、ケミカルアブストラクト（Chemical Abstrac
t）に記載がなく、また、本発明者等の知るかぎりで
は、その他の文献にも記載が見当たらないので、この化
合物は新規化合物であると考えられる。Further, with respect to the 1,9-nonanediol monovinyl ether and 1,9-nonanediol dinyl ether of the present invention, Chemical Abstract (Chemical Abstract)
This compound is considered to be a novel compound, since there is no description in t) and no description can be found in other documents as far as the present inventors know.
【０００５】上記のポリアルキレンジオールジビニルエ
ーテルは、紫外線硬化型樹脂や電子線硬化型樹脂などの
活性放射線硬化型樹脂のカチオン重合性反応性希釈剤と
して知られており、これらの化合物を用いることによっ
て高度に架橋された樹脂を形成させることはできるが、
最近では硬化後の樹脂にさらに反応性を持たせたり、ま
た、該樹脂をさらに変性したりすることが求められるよ
うになった。The above-mentioned polyalkylene diol divinyl ether is known as a cationically polymerizable reactive diluent for an actinic radiation curable resin such as an ultraviolet curable resin or an electron beam curable resin. Although it is possible to form highly crosslinked resins,
Recently, it has been required to make the cured resin more reactive or to further modify the resin.
【０００６】[0006]
【発明が解決すべき課題】本発明者等は、例えば、紫外
線硬化型樹脂や電子線硬化型樹脂などの活性放射線硬化
型樹脂の反応性希釈剤として有用な架橋性単量体、特
に、低臭気、低揮発性、且つ、低皮膚刺激性であって毒
性が低く、また、カチオン重合性が極めて高い等の優れ
た性質を有しており、活性放射線硬化型樹脂の反応性希
釈剤として極めて有用であると共に、上記のような広範
な利用が可能な比較的長鎖のジオールのモノビニルエー
テル及びジビニルエーテルを得ることを目的に研究を行
った。SUMMARY OF THE INVENTION The present inventors have found that a crosslinkable monomer useful as a reactive diluent for an active radiation-curable resin such as an ultraviolet-curable resin or an electron beam-curable resin, especially Odor, low volatility, and low skin irritation, low toxicity, and excellent properties such as extremely high cationic polymerizability. Research was conducted to obtain monovinyl ethers and divinyl ethers of relatively long-chain diols which are useful and can be widely used as described above.
【０００７】その結果、水酸化カリウムの存在下、1,9-
ノナンジオールにアセチレンを反応させると、先ずモノ
ビニルエーテルが生成し、次いで該モノビニルエーテル
が順次ジビニルエーテルになる、逐次反応により反応が
進行すること、適宜の時間で反応を停止させることによ
り、ジビニルエーテルと共にモノビニルエーテルを得る
ことができることを見出し、本発明を完成した。As a result, in the presence of potassium hydroxide, 1,9-
When acetylene is reacted with nonanediol, first, monovinyl ether is formed, and then the monovinyl ether is sequentially turned into divinyl ether.The reaction proceeds by a sequential reaction, and the reaction is stopped at an appropriate time. They have found that monovinyl ether can be obtained, and have completed the present invention.
【０００８】そして、得られた1,9-ノナンジオールモノ
ビニルエーテルを活性放射線硬化型樹脂の反応性希釈剤
として用いると、硬化により形成される樹脂に水酸基を
導入することができ、それにより該樹脂を、例えば、メ
ラミン樹脂、エポキシ樹脂、ポリイソシアネート化合物
などの架橋剤によりさらに架橋することが可能であるこ
と、導入された水酸基に、例えば、グリシジルメタクリ
レート等の水酸基と反応するビニル化合物やポリイソシ
アネート類を反応させてビニル基やイソシアネート基な
どの新たな官能基を導入して該樹脂にさらに新たな反応
性を付与することができること、該水酸基を適当な薬剤
によりアセチル化、エステル化、ハロゲン化等を行い、
該樹脂をさらに変成することもできることなどを見出し
た。When the obtained 1,9-nonanediol monovinyl ether is used as a reactive diluent for an actinic radiation-curable resin, a hydroxyl group can be introduced into the resin formed by curing, whereby the resin is cured. Can be further cross-linked by a cross-linking agent such as a melamine resin, an epoxy resin, and a polyisocyanate compound.Introduced hydroxyl groups, for example, vinyl compounds and polyisocyanates that react with hydroxyl groups such as glycidyl methacrylate To introduce a new functional group such as a vinyl group or an isocyanate group so as to impart further new reactivity to the resin, and to acetylate, esterify, or halogenate the hydroxyl group with an appropriate agent. Do
It has been found that the resin can be further modified.
【０００９】また、得られた1,9-ノナンジオールジニル
エーテルを活性放射線硬化型樹脂の反応性希釈剤として
用いることにより、活性放射線硬化により硬度に架橋さ
れた樹脂を形成しうるカチオン重合性反応性希釈財とし
て極めて有用であることも確認された。Further, by using the obtained 1,9-nonanediol dinyl ether as a reactive diluent for an actinic radiation-curable resin, a cationically polymerizable reaction capable of forming a resin crosslinked to a hardness by actinic radiation curing can be obtained. It was also confirmed that it was extremely useful as a sex diluent.
【００１０】[0010]
【課題を解決するための手段】本発明は、有用な新規化
合物である1,9-ノナンジオールモノビニルエーテル及び
1,9-ノナンジオールジビニルエーテルを提供することを
目的とするものである。SUMMARY OF THE INVENTION The present invention provides useful novel compounds, 1,9-nonanediol monovinyl ether and
An object of the present invention is to provide 1,9-nonanediol divinyl ether.
【００１１】以下、本発明を詳細に説明する。本発明の
新規化合物1,9-ノナンジオールモノビニルエーテル及び
1,9-ノナンジオールジビニルエーテルは、下記一般式
(1)及び(2)で表されるものである。Hereinafter, the present invention will be described in detail. The novel compound of the present invention 1,9-nonanediol monovinyl ether and
1,9-nonanediol divinyl ether has the following general formula
This is represented by (1) and (2).
【００１２】[0012]
【化１】 Embedded image
【００１３】[0013]
【化２】Embedded image
【００１４】上記モノビニルエーテルの生成は、次の反
応式(3)に従うものと考えられ、次いで該モノビニルエ
ーテルは、反応式(4)に従ってジビニルエーテルになる
ものと考えられる。The production of the above monovinyl ether is considered to follow the following reaction formula (3), and then the monovinyl ether is considered to become divinyl ether according to the following reaction formula (4).
【００１５】[0015]
【化３】 Embedded image
【００１６】[0016]
【化４】Embedded image
【００１７】本発明化合物の具体的な合成法としては、
例えば、次のような方法を挙げることができる。As a specific method for synthesizing the compound of the present invention,
For example, the following method can be used.
【００１８】例えば、ステンレス鋼（ＳＵＳ）製の耐圧
反応容器中に、1,9-ノナンジオールを入れて加熱して融
解させた後、反応触媒として、例えば、水酸化カリウ
ム、水酸化ナトリウム等のアルカリ金属水酸化物などの
アルカリ性化合物を、1,9-ノナンジオール１モルに対し
て約19〜380ミリモル添加し、反応容器を密封して、窒
素ガスにより該容器内を置換する。For example, 1,9-nonanediol is put into a pressure-resistant reaction vessel made of stainless steel (SUS), heated and melted, and then a reaction catalyst such as potassium hydroxide or sodium hydroxide is used. About 19 to 380 mmol of an alkaline compound such as an alkali metal hydroxide is added to 1 mol of 1,9-nonanediol, the reaction vessel is sealed, and the inside of the vessel is replaced with nitrogen gas.
【００１９】次いで反応容器にアセチレンを圧入しなが
ら、例えば、3〜10kg/cm2程度の圧力条件下、約110〜14
0℃で反応させる。Then, while pressurizing acetylene into the reaction vessel, for example, under pressure conditions of about 3 to 10 kg / cm 2 , about 110 to 14 kg / cm 2.
React at 0 ° C.
【００２０】反応終了後、反応混合物に蒸留水を添加し
て減圧蒸留することにより、本発明の新規化合物である
1,9-ノナンジオールモノビニルエーテルが水蒸気と共に
溜出し、次いで1,9-ノナンジオールジビニルエーテルが
溜出する。After completion of the reaction, distilled water is added to the reaction mixture and distilled under reduced pressure to obtain the novel compound of the present invention.
The 1,9-nonanediol monovinyl ether distills out with the steam and then the 1,9-nonanediol divinyl ether distills.
【００２１】[0021]
【実施例】以下、実施例により本発明を一層詳細に説明
する。The present invention will be described in more detail with reference to the following examples.
【００２２】実施例 2000mlのＳＵＳ製オートクレーブに、純度99重量％の1,
9-ノナンジオール601.1g（約3.71モル）を仕込み、50℃
で熔融させたのち純度95.6重量％の水酸化カリウム30.0
g（約0.51モル）を添加した。反応容器を密封し、攪拌
しながら120℃まで昇温し、窒素ガスを流速1000ml/min
で流して窒素置換しながら４時間かけて生成する水を溜
去させた。次に反応容器内温を約130℃まで昇温し、ア
セチレンを４〜８kg/cm2で圧入した。逐次アセチレンを
補充して反応容器内圧を約４〜８kg/cm2に保ちながら4.
1時間反応させた。EXAMPLE In a 2000 ml SUS autoclave, 1,99% by weight of 1,
Charge 601.1 g (about 3.71 mol) of 9-nonanediol, 50 ℃
35.6% by weight potassium hydroxide 30.0%
g (about 0.51 mol) was added. The reaction vessel is sealed and heated to 120 ° C. with stirring, and nitrogen gas is flowed at a flow rate of 1000 ml / min.
The resulting water was distilled off over 4 hours while purging with nitrogen. Next, the temperature inside the reaction vessel was raised to about 130 ° C., and acetylene was injected at a pressure of 4 to 8 kg / cm 2 . While maintaining the internal pressure of the reaction vessel at about 4 to 8 kg / cm 2 by successively replenishing acetylene, 4.
The reaction was performed for 1 hour.
【００２３】反応終了後、残留するアセチレンガスをパ
ージして反応液662.3gを得た。ガスクロマトグラフィー
分析の結果、得られた反応液中には1,9-ノナンジオール
モノビニルエーテル43.7重量％および1,9-ノナンジオー
ルジビニルエーテル13.1重量％が含まれていた。これら
の生成物の収率は、原料の1,9-ノナンジオールに対し
て、それぞれ41.9％および11.0％であった。After completion of the reaction, the remaining acetylene gas was purged to obtain 662.3 g of a reaction solution. As a result of gas chromatography analysis, the obtained reaction solution contained 43.7% by weight of 1,9-nonanediol monovinyl ether and 13.1% by weight of 1,9-nonanediol divinyl ether. The yields of these products were 41.9% and 11.0%, respectively, based on the starting 1,9-nonanediol.
【００２４】得られた反応液は、ラシッヒリング充填蒸
留塔付き2000ml三口フラスコに入れ、蒸留水101.2gを加
えて内温172〜202℃、還流比１で精溜することにより、
1,9-ノナンジオールモノビニルエーテル280.3g及び1,9-
ノナンジオールジビニルエーテル84.3gを分離採集し
た。The obtained reaction solution was placed in a 2000 ml three-necked flask equipped with a Raschig ring-filled distillation tower, and 101.2 g of distilled water was added thereto, followed by rectification at an internal temperature of 172 to 202 ° C. and a reflux ratio of 1.
280.3 g of 1,9-nonanediol monovinyl ether and 1,9-
84.3 g of nonanediol divinyl ether was separated and collected.
【００２７】得られた1,9-ノナンジオールモノビニルエ
ーテル及び1,9-ノナンジオールジビニルエーテルの沸
点、並びに、赤外分光分析（ＩＲ）及びＮＭＲ分析の特
性吸収値は次表１のとおりであった。また、ＩＲチャー
トを図１及び図２に示した。なお、赤外分光分析は得ら
れた化合物（液体）を臭化タリウム・ヨウ化タリウム混
晶板（KRS−5）に塗布して測定した。The boiling points of the obtained 1,9-nonanediol monovinyl ether and 1,9-nonanediol divinyl ether, and the characteristic absorption values of infrared spectroscopic analysis (IR) and NMR analysis are as shown in Table 1 below. Was. 1 and 2 show IR charts. In addition, infrared spectroscopy was performed by applying the obtained compound (liquid) to a thallium bromide / thallium iodide mixed crystal plate (KRS-5).
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】本発明の新規化合物1,9-ノナンジオール
モノビニルエーテル及び1,9-ノナンジオールジビニルエ
ーテルは、低臭気、低揮発性、且つ、低皮膚刺激性であ
って毒性が低く、また、カチオン重合性が極めて高い等
の優れた性質を有し、活性放射線硬化型樹脂の反応性希
釈剤として極めて有用であると共に、各種樹脂の改質剤
や架橋剤としても有用である。The novel compounds 1,9-nonanediol monovinyl ether and 1,9-nonanediol divinyl ether of the present invention have low odor, low volatility, low skin irritation and low toxicity, and It has excellent properties such as extremely high cationic polymerizability, and is extremely useful as a reactive diluent for actinic radiation-curable resins, and also as a modifier or cross-linking agent for various resins.
【００３０】本発明の新規化合物である1,9-ノナンジオ
ールモノビニルエーテル及び1,9-ノナンジオールジビニ
ルエーテルを活性放射線硬化型樹脂の反応性希釈剤とし
て用いることによって、前者の場合、硬化後の樹脂中に
水酸基を導入し、また、必要に応じてこの水酸基に、例
えば、グリシジルメタクリレート等の水酸基と反応する
ビニル化合物やポリイソシアネート類を反応させビニル
基やイソシアネート基などの新たな官能基を導入して該
樹脂にさらに反応性を持たせたり、或いは、適当な薬剤
を用いて該水酸基をアセチル化、エステル化、ハロゲン
化等することによって該樹脂を変性することができる。
また、後者の場合には、硬化後高度に架橋された樹脂を
形成することができる。By using 1,9-nonanediol monovinyl ether and 1,9-nonanediol divinyl ether, which are novel compounds of the present invention, as a reactive diluent for an actinic radiation-curable resin, in the former case, Introduce a hydroxyl group into the resin, and if necessary, react a hydroxyl compound such as glycidyl methacrylate with a vinyl compound or polyisocyanate to introduce a new functional group such as a vinyl group or an isocyanate group. Then, the resin can be further made reactive, or the resin can be modified by acetylation, esterification, halogenation, or the like of the hydroxyl group using an appropriate agent.
In the latter case, a highly crosslinked resin can be formed after curing.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の1,9-ノナンジオールモノビニルエーテ
ルのＩＲチャートである。FIG. 1 is an IR chart of 1,9-nonanediol monovinyl ether of the present invention.
【図２】本発明の1,9-ノナンジオールジビニルエーテル
のＩＲチャートである。FIG. 2 is an IR chart of 1,9-nonanediol divinyl ether of the present invention.
【化２】 Embedded image
【化２】 Embedded image
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 43/16 C07C 43/178 ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continued on the front page (58) Fields surveyed (Int. Cl. 6 , DB name) C07C 43/16 C07C 43/178 CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-131580 | 1991-05-08 | ||
| JP13158091 | 1991-05-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05279284A JPH05279284A (en) | 1993-10-26 |
| JP2953545B2 true JP2953545B2 (en) | 1999-09-27 |
Family
ID=15061380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14199692A Expired - Lifetime JP2953545B2 (en) | 1991-05-08 | 1992-05-08 | 1,9-nonanediol monovinyl ether and 1,9-nonanediol divinyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2953545B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015190376A1 (en) * | 2014-06-13 | 2015-12-17 | 丸善石油化学株式会社 | Novel divinyl ether compound and method for producing same |
| WO2020111030A1 (en) * | 2018-11-27 | 2020-06-04 | 丸善石油化学株式会社 | Method for producing divinyl ether compound having alkylene skeleton |
| EP3889126A4 (en) * | 2018-11-27 | 2022-08-17 | Maruzen Petrochemical Co., Ltd. | Method for producing divinyl ether compound having alkylene skeleton |
-
1992
- 1992-05-08 JP JP14199692A patent/JP2953545B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05279284A (en) | 1993-10-26 |
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