JPS6335541A - Production of chloroformate containing (meth)acryloyl group at molecular end - Google Patents
Production of chloroformate containing (meth)acryloyl group at molecular endInfo
- Publication number
- JPS6335541A JPS6335541A JP17877686A JP17877686A JPS6335541A JP S6335541 A JPS6335541 A JP S6335541A JP 17877686 A JP17877686 A JP 17877686A JP 17877686 A JP17877686 A JP 17877686A JP S6335541 A JPS6335541 A JP S6335541A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- phosgene
- ether
- reaction
- 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.)
- Pending
Links
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 title claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- WNGWIBINRGUHSN-UHFFFAOYSA-N 2-carbonochloridoyloxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(Cl)=O WNGWIBINRGUHSN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 150000004651 carbonic acid esters Chemical class 0.000 abstract 1
- -1 carbonate ester Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 150000002170 ethers Chemical class 0.000 description 8
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- PBTDMHUAEDVFPJ-UHFFFAOYSA-N 2-carbonochloridoyloxyethyl prop-2-enoate Chemical compound ClC(=O)OCCOC(=O)C=C PBTDMHUAEDVFPJ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、分子末端に（メタ）アクリロイル基を有する
クロロホーメートの製造法に関する。さらに詳しくは、
水酸基を有する（メタ）アクリレートとホスゲンとを反
応させてクロロホーメートを製造するに際して、反応助
剤としてエーテル類を使用する方法である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a chloroformate having a (meth)acryloyl group at the end of the molecule. For more details,
This is a method in which ethers are used as reaction aids when producing chloroformates by reacting (meth)acrylates having hydroxyl groups with phosgene.
水酸基を有する（メタ）アクリレート、例えば、２−ヒ
ドロキシエチルメタクリレート（以下、２−２−１１Ｈ
と記すことがある。）とホスゲンとを反応させてえられ
るメタクリロキシエチルクロロホーメートは、活性な水
素と反応するＣＩ基を有しており、かつ分子末端に重合
性の不飽和基を有していることから、架橋用モノマーと
して、また炭酸エステル用原料として、高分子分野、有
機合成分野において使用される有用な化合物である。(Meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl methacrylate (hereinafter referred to as 2-2-11H
It is sometimes written as ) and phosgene, methacryloxyethyl chloroformate has a CI group that reacts with active hydrogen and has a polymerizable unsaturated group at the end of the molecule. It is a useful compound used in the polymer field and organic synthesis field as a crosslinking monomer and as a raw material for carbonate ester.
従来、ホスゲンを用いたアルコール類のクロロホーメー
トは、一般に次の様にして製造される。Conventionally, chloroformates of alcohols using phosgene are generally produced as follows.
（１）アルコールとホスゲンとを直接反応させる。(1) Directly react alcohol and phosgene.
（２）有機溶媒の存在下、アルコールとホスゲンとを反
応させる。(2) Alcohol and phosgene are reacted in the presence of an organic solvent.
（３）有機溶媒および塩基物質の存在下、アルコールと
ホスゲンとを反応させる。(3) Alcohol and phosgene are reacted in the presence of an organic solvent and a basic substance.
（１）の方法は、例えば英国特許第６２９０９１号に記
載されている。この方法は溶媒を使用しないので、反応
後の後処理が簡単であるが、残念ながら塩素化クロロホ
ーメートが相当量副生ずるので好ましくない。Method (1) is described, for example, in British Patent No. 629091. Since this method does not use a solvent, post-treatment after the reaction is simple, but unfortunately a considerable amount of chlorinated chloroformate is produced as a by-product, which is not preferable.
（３）の方法は、例えば特開昭５３−７３５２１号に記
載されている。この方法は前記の方法に比べて好収率で
メタクリロキシエチルクロロホーメートの如きクロロホ
ーメート類を得ることができるが、酸受体としてアミン
頚を用いる為にアミンの塩酸塩を多量に生じ、工業的見
地からすると、アミンの塩酸塩よりアミンの回収工程を
必要とし有利な方法とは言えない。Method (3) is described, for example, in Japanese Patent Application Laid-open No. 73521/1983. This method can obtain chloroformates such as methacryloxyethyl chloroformate in a better yield than the above method, but because it uses an amine neck as an acid acceptor, a large amount of amine hydrochloride is produced. From an industrial standpoint, this method cannot be said to be advantageous since it requires a step of recovering the amine compared to the amine hydrochloride.
また、（２）の方法として、−船釣な溶媒、例えば、ベ
ンセン、トルエン、塩化メチレン、四塩化炭素、クロル
ベンゼン、ヘキサン、シクロヘキサン、酢酸エチル、等
を用いて２−２−１１Ｈとホスゲンとを反応させた場合
、副生ずる塩化水素が二重結合やＯ１＋基と反応し塩素
化クロロホーメートや目的物とは異なった塩素化物を多
量に生成し、目的物のクロロホーメートは多くても６５
％程度に過ぎない。In addition, as method (2), 2-2-11H and phosgene are combined using a suitable solvent such as benzene, toluene, methylene chloride, carbon tetrachloride, chlorobenzene, hexane, cyclohexane, ethyl acetate, etc. When reacting, the by-produced hydrogen chloride reacts with double bonds and O1+ groups, producing a large amount of chlorinated chloroformate and other chlorinated products that are different from the target product, and the target chloroformate is at most 65
It is only about %.
本発明者らは、上記した従来方法に認められる問題点に
鑑み種々検討した結果、反応助剤として特定のエーテル
類を用いて反応させることにより、高収率で、高純度な
りロワホーメート類を容易に製造することができること
を見出し本発明を為した。As a result of various studies in view of the problems observed in the conventional methods described above, the present inventors have found that lower formates can be easily produced with high yield and high purity by reacting with specific ethers as reaction aids. The present invention has been made based on the discovery that it can be produced.
すなわち、本発明は反応助剤としてエーテル類の存在下
に、水酸基を有する（メタ）アクリレートとホスゲンと
を反応させることを特徴とする分子末端に（メタ）アク
リロイル基を有するクロロホーメートの製造法である。That is, the present invention provides a method for producing a chloroformate having a (meth)acryloyl group at the molecular terminal, which is characterized by reacting a (meth)acrylate having a hydroxyl group with phosgene in the presence of an ether as a reaction aid. It is.
本発明においては、反応助剤としてエーテル類が使用さ
れるが、このエーテル類は上記した如きの一般の有機溶
媒とは全く別の挙動を示し、水酸基を有する （メタ）
アクリレートとホスゲンとを反応させた場合、反応に伴
って副生ずる塩化水素の二重結合やＯ１＋基への反応を
阻止し目的物以外の塩素化物の副生を大幅に抑制する。In the present invention, ethers are used as reaction aids, but these ethers behave completely differently from the general organic solvents mentioned above and have hydroxyl groups (meth).
When acrylate and phosgene are reacted, the reaction of hydrogen chloride produced as a by-product with the reaction to double bonds and O1+ groups is inhibited, thereby significantly suppressing the production of chlorinated products other than the target product.
本発明において使用されるエーテル類としては、その沸
点が余りに高いものは、反応後目的物との分離の際に目
的生成物が重合を起こしたりして好ましくなく、また逆
に沸点が余りに低いものは取り扱い上危険性が伴い好ま
しくないことから、テトラヒドロフラン、テトラヒドロ
ビラン、ジイソプロピルエーテル、ジエチルエーテル、
ジオ ′キサン等があげられるが、これらの中、特にテ
トラヒドロフラン（以下、ＴＨＦと記すことがある。）
が反応率および得られるクロロホーメートの純度などの
点から好適である。Regarding the ethers used in the present invention, those with a boiling point that is too high are undesirable because the target product may polymerize when separated from the target product after the reaction, and conversely, those with a boiling point that are too low are undesirable. Tetrahydrofuran, tetrahydrobilane, diisopropyl ether, diethyl ether,
Among these, tetrahydrofuran (hereinafter sometimes referred to as THF) is mentioned.
is preferable from the viewpoint of reaction rate and purity of the obtained chloroformate.
本発明において反応助剤としてのエーテル類の使用量は
多い方が好ましいが、工業的見地からその使用量はおの
ずと制限され、通常、（メタ）アクリレートに対して重
遣割合で０．２〜２０倍、好ましくは１〜４倍で用いら
れる。なお、上記のエーテル類と共に一般の有機溶媒を
併用することもできる。In the present invention, it is preferable to use a large amount of ether as a reaction aid, but the amount used is naturally limited from an industrial standpoint, and is usually 0.2 to 20% by weight relative to (meth)acrylate. It is used at a ratio of 1 to 4 times, preferably 1 to 4 times. In addition, general organic solvents can also be used together with the above-mentioned ethers.
本発明方法において反応温度は、使用される（メタ）ア
クリレート頚および生成物の重合性などを考慮して決め
られるが、一般には余り高くない方が良く、通常−２０
〜５０℃、好ましくは０〜２０℃である。In the method of the present invention, the reaction temperature is determined taking into consideration the (meth)acrylate neck used and the polymerizability of the product, but it is generally better not to be too high, and is usually -20
-50°C, preferably 0-20°C.
ホスゲンの使用ｍは（メタ）アクリレートに対してモル
比で１〜１．５倍、好ましくは１．１〜１．２倍程度で
充分である。The molar ratio of phosgene to (meth)acrylate is 1 to 1.5 times, preferably 1.1 to 1.2 times.
本発明において使用される （メタ）アクリレートとし
ては一般式
ＣＩｌ□＝Ｃ−ＣＯＲ２０１１（Ｒ，は水素、またはメ
チル基、■
ＯＲ２は０２〜ＣＩＯの直鎮または有枝アルキレン基、
または酸素を１〜
５個含むエーテル基を示す。）
であって、たとえば、２−ヒドロキシエチル（メタ）ア
クリレート、２−ヒドロキシプロピル（メタ）アクリレ
ート、１−ヒドロキシプロピル（メタ）アクリレート、
３−ヒドロキシブチル（メタ）アクリレート、４−ヒド
ロキシブチル（メタ）アクリレート、６−ヒドロキシヘ
キシル（メタ）アクリレート、（メタ）アクリル酸ジエ
チレングリコールモノエステル、（メタ）アクリル酸ジ
プロピレングリコールモノエステル等が例示される。The (meth)acrylate used in the present invention has the general formula CIl□=C-COR2011 (R is hydrogen or a methyl group, ■OR2 is a straight or branched alkylene group of 02 to CIO,
Or it represents an ether group containing 1 to 5 oxygen atoms. ), for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate,
Examples include 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid diethylene glycol monoester, (meth)acrylic acid dipropylene glycol monoester, etc. Ru.
これら（メタ）アクリレート類とホスゲンとを反応させ
る方法は、ホスゲンのエーテル類溶液、特にＴＨＦ溶液
に（メタ）アクリレートを添加する方法、あるいは（メ
タ）アクリレート類のエーテル類溶液、特にＴＨＦ溶液
にホスゲンを導入する方法のいずれも採用できるが、工
業的製造の点からは後者の方法が好ましい態様である。These (meth)acrylates and phosgene can be reacted by adding (meth)acrylate to an ether solution of phosgene, especially a THF solution, or by adding phosgene to an ether solution of (meth)acrylates, especially a THF solution. Although any method of introducing can be adopted, the latter method is a preferred embodiment from the point of view of industrial production.
なお、市販の（メタ）アクリレ−）Ｍには一般には重合
禁止剤が添加されているが、反応時あるいは生成物の後
処理時の重合を考慮し、重合禁止剤をさらに添加するこ
とが好ましい。In addition, a polymerization inhibitor is generally added to commercially available (meth)acrylate)M, but it is preferable to further add a polymerization inhibitor in consideration of polymerization during the reaction or post-treatment of the product. .
反応後、反応溶液中に残存するホスゲンおよび反応に伴
って副生ずる塩化水素を窒素等の不活性ガスを吹き込み
除去後、使用したエーテル類（ＴＨＦ）を蒸留により留
去することにより、９５％以上の高純度で目的とするク
ロロホーメート類を得るこきができる。エーテル類（Ｔ
ＨＦ）の留去は一般には減圧下に実施される。この際の
温度は低い方が好ましく、通常７０℃以下、好ましくは
５０℃以下で実施するように減圧度を適宜調節すること
が必要である。After the reaction, phosgene remaining in the reaction solution and hydrogen chloride produced as a by-product during the reaction are removed by blowing in an inert gas such as nitrogen, and the ethers (THF) used are distilled off to achieve a concentration of 95% or more. It is possible to obtain the desired chloroformates with high purity. Ethers (T
The distillation of HF) is generally carried out under reduced pressure. The temperature at this time is preferably lower, and it is necessary to adjust the degree of reduced pressure appropriately so that the temperature is usually 70°C or lower, preferably 50°C or lower.
本発明によれば、副反応生成物を殆ど生成させることな
く、簡単な方法で収率良く高純度の目的とするクロロホ
ーメート類を製造することができ、工業的に極めて意義
有る方法である。According to the present invention, the desired chloroformates can be produced in high yield and purity in a simple manner without producing nearly any side reaction products, and this is a method of great industrial significance. .
以下に本発明の実施例を示す。Examples of the present invention are shown below.
実施例 Ｉ
Ｔ ＨＦ２６１ｇに２−ＨＥＭＡ ６６ｇ （０，５１
モル）を溶解し、温度１℃でホスゲン６０．３ｇ （０
，６１モル）を、４．５時間を要して該溶液に吹き込ん
だ。反応後、反応液からＴＨＦを減圧下に留去し、純度
９８％のメタクリロキシエチルクロロホーメートを９５
．５ｇ得た。Example I T 261 g of HF and 66 g of 2-HEMA (0,51
60.3 g (0 mol) of phosgene was dissolved at a temperature of 1°C.
, 61 mol) was bubbled into the solution over a period of 4.5 hours. After the reaction, THF was distilled off from the reaction solution under reduced pressure to obtain 98% pure methacryloxyethyl chloroformate.
．． I got 5g.
なお、生成物の純度はガスクロマトグラフィー分析によ
り求めた。（以下同様）
実施例 ２
温度０℃でＴ ＨＦ ９３ｇにホスゲン６７ｇ （０，
６８モル）を吹き込んだ後、これに２−２−１１Ｅ ８
０ｇ （０，６２モル）を１０分を要して滴下したのち
、０℃〜２０℃の温度で１．５時間攪拌した。反応終了
後ＴＨＦを減圧下に留去し、純度９７．１％のメタクリ
ロキシエチルクロロホーメートを１１５ｇ得た。Note that the purity of the product was determined by gas chromatography analysis. (Similarly below) Example 2 67 g of phosgene (0,
After blowing in 2-2-11E 8
After 0 g (0.62 mol) was added dropwise over 10 minutes, the mixture was stirred at a temperature of 0°C to 20°C for 1.5 hours. After the reaction was completed, THF was distilled off under reduced pressure to obtain 115 g of methacryloxyethyl chloroformate with a purity of 97.1%.
実施例 ３
Ｔ ＨＦ １８６ｇに２−ヒドロキシエチルアクリレー
ト６２ ｇ（０，５３モル）を溶解し、温度０℃でホス
ゲン６３ｇ （０，６４モル）を４時間を要して該溶液
に吹き込んだ。反応後、反応液からＴＨＦを減圧下に留
去し、純度９８％のアクリロキシエチルクロロホーメー
トを９３ｇ得た。Example 3 62 g (0.53 mol) of 2-hydroxyethyl acrylate was dissolved in 186 g of THF, and 63 g (0.64 mol) of phosgene was bubbled into the solution over a period of 4 hours at a temperature of 0°C. After the reaction, THF was distilled off from the reaction solution under reduced pressure to obtain 93 g of acryloxyethyl chloroformate with a purity of 98%.
実施例 ４
Ｔ ＨＦ ２１０ｇにメタクリル酸ジエチレングリコー
ルモノエステル７０ｇ （０，４０モ）Ｉ／′）を溶解
し、温度２℃でホスゲン５１ｇ （０，５１モル）を３
．５時間を要して該溶液に吹き込んだ。反応後、反応液
からＴＨＦを減圧下に留去して純度９５％のメタクリロ
キシエチル−クロロホルミルエチルエーテル９０ｇ ヲ
得り。Example 4 70 g (0,40 mo) I/') of diethylene glycol methacrylate was dissolved in 210 g of THF, and 51 g (0,51 mo) of phosgene was dissolved at 2°C.
．． The solution was bubbled for 5 hours. After the reaction, THF was distilled off from the reaction solution under reduced pressure to obtain 90 g of methacryloxyethyl-chloroformylethyl ether with a purity of 95%.
比較例 １
塩化メチレン２６５ｇに２−ＨＥＭＡ ６６ ｇ （０
，６１モル）を溶解し、これに１℃でホスゲン６０．３
ｇ （０゜６１モル）を４時間を要して導入した。反
応後塩化メチレンを減圧下に除去し、純度４０．５％の
メタクリロキシエチルクロロホーメートを１１０ｇ得た
。原料２−＋１１ＥＭＡは認められなかった。Comparative Example 1 2-HEMA 66 g (0
, 61 mol) and 60.3 mol of phosgene at 1°C.
g (0.61 mol) was introduced over a period of 4 hours. After the reaction, methylene chloride was removed under reduced pressure to obtain 110 g of methacryloxyethyl chloroformate with a purity of 40.5%. Raw material 2-+11 EMA was not observed.
比較例 ２
実施例１のＴ ＨＦの代わりにシクロヘキサン２６０ｇ
を使用した以外は実施例１と同様に実施した。純度６３
％メタクリロキシエチルクロロホーメートを１０５ｇ得
た。原料２−２−１１１Ｅは認められなかった。Comparative Example 2 260g of cyclohexane instead of THF in Example 1
The same procedure as in Example 1 was carried out except that . Purity 63
% methacryloxyethyl chloroformate was obtained. Raw material 2-2-111E was not observed.
特許出願人 三菱瓦斯化学株式会社 代理人 弁理士 小 堀 貞 文 手続補正書 昭和６２年３月２日Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Agent: Patent attorney Sadafumi Kohori Procedural amendment March 2, 1986
Claims (3)
有する（メタ）アクリレートとホスゲンとを反応させる
ことを特徴とする分子末端に（メタ）アクリロイル基を
有するクロロホーメートの製造法。(1) A method for producing a chloroformate having a (meth)acryloyl group at the end of the molecule, which comprises reacting a (meth)acrylate having a hydroxyl group with phosgene in the presence of an ether as a reaction aid.
の範囲第１項記載の方法。(2) The method according to claim 1, wherein the ether is tetrahydrofuran.
式で表される化合物である特許請求の範囲第１項記載の
方法。 ▲数式、化学式、表等があります▼ （Ｒ＿１は水素、またはメチル基、 Ｒ＿２はＣ＿２〜Ｃ＿１＿０の直鎖または有枝アルキレ
ン基、または酸素を１〜５個含むエーテル基を示す。）(3) The method according to claim 1, wherein the (meth)acrylate having a hydroxyl group is a compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1 is hydrogen or a methyl group, R_2 is a C_2 to C_1_0 linear or branched alkylene group, or an ether group containing 1 to 5 oxygen atoms.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17877686A JPS6335541A (en) | 1986-07-31 | 1986-07-31 | Production of chloroformate containing (meth)acryloyl group at molecular end |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17877686A JPS6335541A (en) | 1986-07-31 | 1986-07-31 | Production of chloroformate containing (meth)acryloyl group at molecular end |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6335541A true JPS6335541A (en) | 1988-02-16 |
Family
ID=16054427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17877686A Pending JPS6335541A (en) | 1986-07-31 | 1986-07-31 | Production of chloroformate containing (meth)acryloyl group at molecular end |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6335541A (en) |
-
1986
- 1986-07-31 JP JP17877686A patent/JPS6335541A/en active Pending
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