JPS63196544A - Production of fluorinated alkyl (meth)acrylates - Google Patents
Production of fluorinated alkyl (meth)acrylatesInfo
- Publication number
- JPS63196544A JPS63196544A JP62027258A JP2725887A JPS63196544A JP S63196544 A JPS63196544 A JP S63196544A JP 62027258 A JP62027258 A JP 62027258A JP 2725887 A JP2725887 A JP 2725887A JP S63196544 A JPS63196544 A JP S63196544A
- Authority
- JP
- Japan
- Prior art keywords
- fluorinated alkyl
- oxide
- bis
- meth
- catalyst
- 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
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 150000003606 tin compounds Chemical class 0.000 claims abstract 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 4
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 229950000688 phenothiazine Drugs 0.000 abstract description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 alkali metal alkoxides Chemical class 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UIQCRIFSBWGDTQ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F UIQCRIFSBWGDTQ-UHFFFAOYSA-N 0.000 description 2
- WCFUQBKWMVPFHY-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9-heptadecafluorodecan-1-ol Chemical compound CC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(O)(F)F WCFUQBKWMVPFHY-UHFFFAOYSA-N 0.000 description 2
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 2
- JLHADLTXDDGZFX-UHFFFAOYSA-L [[acetyloxy(dibutyl)stannyl]oxy-dibutylstannyl] acetate Chemical compound CCCC[Sn](CCCC)(OC(C)=O)O[Sn](CCCC)(CCCC)OC(C)=O JLHADLTXDDGZFX-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- JQTLQMOFVUEIKU-UHFFFAOYSA-M dibutyl(dodecanoyloxy)tin Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)CCCC JQTLQMOFVUEIKU-UHFFFAOYSA-M 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- LPRFOPMQPYJAES-UHFFFAOYSA-M C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCC)[Sn+]CCCCCCCC Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCC)[Sn+]CCCCCCCC LPRFOPMQPYJAES-UHFFFAOYSA-M 0.000 description 1
- ZRDBFQOXYSEDAW-UHFFFAOYSA-M CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)CCCC Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Sn](CCCC)CCCC ZRDBFQOXYSEDAW-UHFFFAOYSA-M 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- IRCUSRKMPCOMRN-UHFFFAOYSA-M dioctyltin(1+);acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)CCCCCCCC IRCUSRKMPCOMRN-UHFFFAOYSA-M 0.000 description 1
- FHEQTPVGRGPNHS-UHFFFAOYSA-M dioctyltin(1+);dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)CCCCCCCC FHEQTPVGRGPNHS-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はエステル交換反応によりフッ素化アルキル（メ
タ）アクリレート類を製造する方法に関し、特にそれに
用いるエステル交換触媒に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing fluorinated alkyl (meth)acrylates by a transesterification reaction, and particularly to a transesterification catalyst used therein.
［従来の技術］
従来、この種のエステル交換反応に用いられる触媒とし
ては、ナトリウムアルコキサイドに代表されるアルカリ
金属アルコキサイド、チタンアルコキサイド、ジアルキ
ルスズオキサイドなどが公知であった。[Prior Art] Conventionally, alkali metal alkoxides such as sodium alkoxide, titanium alkoxides, dialkyltin oxides, and the like have been known as catalysts used in this type of transesterification reaction.
［発明が解決しようとする問題点］
しかしながら、これらの触媒は以下のような問題点を有
していた。[Problems to be Solved by the Invention] However, these catalysts had the following problems.
すなわち、アルカリ金属°アルコキサイドは反応中に触
媒活性が失活しやすいこと、メチルアクリレートまたは
メチルメタクリレートの二重結合にフッ素化アルキルア
ルコールや生成メタノールがマイケル付加して、副生成
物ができやすいこと。In other words, the catalytic activity of alkali metal alkoxides tends to be deactivated during the reaction, and the fluorinated alkyl alcohols and methanol produced tend to undergo Michael addition to the double bonds of methyl acrylate or methyl methacrylate, resulting in the formation of by-products.
反応中に重合を促進するため、反応釜にポリマーが付着
すること、触媒の再利用が不可能であること、また洗浄
工程が必要となることなどの問題があった。In order to promote polymerization during the reaction, there were problems such as polymer adhesion to the reaction vessel, reuse of the catalyst was impossible, and a cleaning step was required.
またチタンアルコキサイドは反応系内の微量水分により
失活するため、事前に脱水工程が必要となること、高価
であること、また洗浄工程が必要であることなどの問題
があった。Furthermore, since titanium alkoxide is deactivated by trace amounts of water in the reaction system, there are problems such as requiring a dehydration step in advance, being expensive, and requiring a washing step.
またジアルキルスズオキサイドは触媒活性が失活しやす
く、リサイクル使用できないこと、高価であることなど
の問題点があった。Further, dialkyl tin oxides have problems such as their catalytic activity is easily deactivated, they cannot be recycled, and they are expensive.
本発明は以上のような問題点の解決を目的とする。すな
わち、エステル交換反応によりフッ素化アルキル（メタ
）アクリレートを製造するに際し、触媒として、反応系
中の微量水分に影響されず、触媒活性が低下せず、副反
応を引き起こさず、洗浄工程が不要で、また触媒として
再使用の可能な物質を用いて、高収率で高純度の目的物
を製造することを目的とする。The present invention aims to solve the above problems. In other words, when producing fluorinated alkyl (meth)acrylates by transesterification, it can be used as a catalyst without being affected by trace amounts of water in the reaction system, without reducing catalyst activity, without causing side reactions, and without the need for a cleaning step. , and also aims to produce a target product with high yield and high purity using a reusable substance as a catalyst.
［問題点を解決するための手段および作用］未発０１１
４ｆＹ（ＣＸ？）ｎｃＨ２０Ｈ（Ｘ、 Ｙは水素または
フッ素で、その内少なくとも３個以上がフッ素）で表わ
されるフッ素化アルキルアルコールと、メ（Ｒは水素ま
たはメチル基）で示されるフッ素化アルキル（メタ）ア
クリレート類を製造するに際し、触媒として一般式ＣＩ
）
（ＲＪ、 Ｒ２，Ｒ３，Ｒ４はＣ４〜Ｃ８のアルキル基
。[Means and actions for solving the problem] Unissued 011
A fluorinated alkyl alcohol represented by 4fY(CX?)ncH20H (X, Y are hydrogen or fluorine, at least three of which are fluorine), and a fluorinated alkyl alcohol represented by M (R is hydrogen or methyl group) When producing meth)acrylates, general formula CI is used as a catalyst.
) (RJ, R2, R3, and R4 are C4 to C8 alkyl groups.
Ｒ５はＣ１〜Ｃ１ｌのアルキル基）
で表わされる有機スズ化合物を用いることを特徴とする
フッ素化アルキル（メタ）アクリレート類の製造方法で
ある。This is a method for producing fluorinated alkyl (meth)acrylates, characterized in that R5 is an alkyl group of C1 to C11.
本発明に用いるエステル交換触媒ＣＩ）は、塩ビの安定
剤や農薬原料として市販されており、容易に入手できる
。この触媒は反応系中の微量水分に影響されないので事
前の脱水工程が不要であること１反応生触媒活性が低下
しないので反応時間が短かいこと、副反応を引き起こさ
ないこと、洗浄工程が不要であること、また、蒸留残渣
を反応にリサイクルすると、再び触媒として使用可能で
あることなどの特長を有する。The transesterification catalyst CI) used in the present invention is commercially available as a stabilizer for vinyl chloride and as a raw material for agricultural chemicals, and is easily available. This catalyst is not affected by trace amounts of water in the reaction system, so there is no need for a prior dehydration step. 1. The reaction time is short because the reaction live catalyst activity does not decrease, it does not cause side reactions, and there is no need for a washing step. Furthermore, if the distillation residue is recycled into the reaction, it can be used again as a catalyst.
本発明に用いられる一般式（Ｉ）のエステル交換触媒と
し′ては、例えばビス（ジブチルアセトキシスズ）オキ
サイド、ビス（ジブチルオクタノイルオキシスズ）オキ
サイド、ビス（ジブチルラウロイルオキシスズ）オキサ
イド、ビス（ジブチルステアロイルオキシスズ）オキサ
イド、ビス（ジオクチルアセトキシスズ）オキサイド、
ビス（ジオクチルオクタノイルオキシスズ）オキサイド
、ビス（ジオクチルラウロイルオキシスズ）オキサイド
、ビス（ジオクチルステアロイルオキシスズ）オキサイ
ドなどが挙げられるが、特にビス（ジブチルオクタノイ
ルオキシスズ）オキサイド、ビス（ジブチルラウロイル
オキシスズ）オキサイド、ビス（ジブチルステアロイル
オキシスズ）オキサイドからなる群より少なくとも１種
を用いるのが好ましい、これらの触媒の使用量は、フッ
素化アルキルアルコールに対し０．１〜５．０モル％、
好ましくは０．２５〜２．５モル％用いるのが良い。Examples of the transesterification catalyst of general formula (I) used in the present invention include bis(dibutyl acetoxytin) oxide, bis(dibutyl octanoyloxytin) oxide, bis(dibutyl lauroyloxytin) oxide, bis(dibutyl Stearoyloxytin) oxide, bis(dioctyl acetoxytin) oxide,
Bis(dioctyl octanoyloxytin) oxide, bis(dioctyl lauroyl oxytin) oxide, bis(dioctyl stearoyl oxytin) oxide, etc., but especially bis(dibutyl octanoyl oxytin) oxide, bis(dibutyl lauroyl oxytin) ) oxide, bis(dibutylstearoyloxytin) oxide, and the amount of these catalysts used is 0.1 to 5.0 mol% based on the fluorinated alkyl alcohol.
It is preferable to use 0.25 to 2.5 mol%.
本発明の製造方法においては、原料のメチル（メタ）ア
クリレートは、原料のフッ素化アルキルアルコール１モ
ルに対し、１．２〜８．０モル、好ましくは２．０〜５
．０モル用いるのが良い。In the production method of the present invention, the raw material methyl (meth)acrylate is 1.2 to 8.0 mol, preferably 2.0 to 5 mol, per 1 mol of the raw material fluorinated alkyl alcohol.
．． It is better to use 0 mol.
本発明の製造方法は、重合防止剤の存在下に行なうこと
が好ましく、例えばフェノチアジン、ハイドロキノンモ
ノメチルエーテルなどが挙げられ、原料のフッ素化アル
キルアルコールに対し１００〜５０００ｐｐ■、好まし
くは２００〜２０００ｐｐｍ用いるのが良い。The production method of the present invention is preferably carried out in the presence of a polymerization inhibitor, such as phenothiazine, hydroquinone monomethyl ether, etc., and is used in an amount of 100 to 5000 ppm, preferably 200 to 2000 ppm, based on the raw material fluorinated alkyl alcohol. is good.
また、反応温度は７０〜１３０℃の範囲内で行なうのが
好ましい、７０℃以下では触媒活性が低く、１３０℃以
上では重合が起きやすくなる。Further, the reaction temperature is preferably carried out within the range of 70 to 130°C. Below 70°C, the catalyst activity is low, and above 130°C, polymerization tends to occur.
また、反応溶媒としてベンゼン、トルエン、ヘキサンな
どを必要に応じて使用することもできる。Moreover, benzene, toluene, hexane, etc. can also be used as a reaction solvent, if necessary.
［実施例］
実施例１
攪拌機、温度計およびオールダシ璽つ１０段の蒸留塔を
備えたフラスコ中にメチルメタクリレート２５０ｇ （
２，５８８モル）、オクタフルオロペンタノール１５０
ｇ （０，６４７モル）、ｎ−ヘキサン５０ｇ、重合防
止剤としてフェノチアジン０．２５９ｇ、触媒としてビ
ス（ジブチルラウロイルオキシスズ）オキサイド４．５
ｇを入れ、攪拌しつつ加熱した。共沸してくるメタノー
ルとへキサンの混合物をデカンタ−で静置し、ｎ−ヘキ
サン層を塔へ戻し、メタノール層を抜き出すことによっ
て、連続的に反応を進めた。[Example] Example 1 250 g of methyl methacrylate (
2,588 mol), octafluoropentanol 150
g (0,647 mol), 50 g of n-hexane, 0.259 g of phenothiazine as a polymerization inhibitor, and 4.5 g of bis(dibutyllauroyloxytin) oxide as a catalyst.
g and heated while stirring. The azeotropic mixture of methanol and hexane was allowed to stand in a decanter, the n-hexane layer was returned to the tower, and the methanol layer was extracted to proceed with the reaction continuously.
反応は１１時間行ない、この間の塔頂温度は５６〜５８
℃、ボトム温度は９６〜１０３℃であった。The reaction was carried out for 11 hours, during which the tower top temperature was 56-58
℃, and the bottom temperature was 96-103℃.
反応後、反応混合物をそのまま減圧蒸留し、５５〜５６
℃１５膳ａｕｇにおいて留分１８３．３ｇを得た。この
留分をガスクロマトグラフィー、ＮＭＲ，ＩＲによって
分析したところ、オクタフルオロペンチルメタクリレー
トであることが確認された。After the reaction, the reaction mixture was directly distilled under reduced pressure to obtain 55-56
183.3 g of a fraction was obtained at 15 aug. When this fraction was analyzed by gas chromatography, NMR, and IR, it was confirmed that it was octafluoropentyl methacrylate.
オクタフルオロペンチルメタクリレートの収率は原料の
オクタフルオロペンタノールに対して９６．８％で、ガ
スクロマトグラフィー分析による生成物の純度は９９．
８Ｅｉ％であった。The yield of octafluoropentyl methacrylate was 96.8% based on the raw material octafluoropentanol, and the purity of the product as determined by gas chromatography analysis was 99.
It was 8Ei%.
実施例２
実施例１に述べた装置を用い、メチルメタクリレート１
７２．６ｇ （１，７２４モル）、ヘプタデカフルオロ
デカノール２００ｇ （０，４３１モル） 、 ＩＩ−
ヘキサン２００ｇ、重合防止剤としてフェノチアジン０
．２２８ｇ、触媒としてビス（ジブチルオクタノイルオ
キシスズ）オキサイド６．０ｇを入れ、攪拌しつつ加熱
した０反応は７．０時間行ない、この間の塔頂温度は５
６〜５８℃、ボトル温度は７４〜７５℃であった。Example 2 Using the apparatus described in Example 1, methyl methacrylate 1
72.6 g (1,724 mol), heptadecafluorodecanol 200 g (0,431 mol), II-
200g hexane, 0 phenothiazine as polymerization inhibitor
．． 228 g, and 6.0 g of bis(dibutyl octanoyloxytin) oxide as a catalyst were added, and the reaction was heated with stirring for 7.0 hours, during which time the top temperature was 5.
The bottle temperature was 74-75°C.
反応後、反応混合物をそのまま減圧蒸留し、１０７〜ｂ
た。この留分をガスクロマトグラフィー、ＮＭＲｌＩＲ
によって分析したところ、ヘプタデカフルオロデシルメ
タクリレートであることが確認された。After the reaction, the reaction mixture was directly distilled under reduced pressure to obtain 107-b. This fraction was analyzed by gas chromatography, NMRlIR
When analyzed, it was confirmed that it was heptadecafluorodecyl methacrylate.
ヘプタデカフルオロデシルメタクリレートの収率は原料
のへブタデカフルオロデカノールに対して９６．０％で
、ガスクロマトグラフィー分析による生成物の純度は９
９．７２％であった。The yield of heptadecafluorodecyl methacrylate was 96.0% based on the raw material heptadecafluorodecanol, and the purity of the product by gas chromatography analysis was 9.
It was 9.72%.
実施例３〜１１
触媒として、ビス（ジブチルオクタノイルオキシスズ）
オキサイド、ビス（ジブチルラウロイルオキシスズ）オ
キサイド、ビス（ジブチルステアロイルオキシスズ）オ
キサイド、ビス（ジブチルアセトキシスズ）オキサイド
、ビス（ジオクチルラウロイルオキシスズ）オキサイド
を用い、フッ素化アルキルアルコールと原料エステルの
組み合わせを種々変化させて、実施例１と同様にして種
々のフッ素化アルキル（メタ）アクリレートを製造した
。Examples 3 to 11 Bis(dibutyloctanoyloxytin) as a catalyst
oxide, bis(dibutyllauroyloxytin) oxide, bis(dibutylstearoyloxytin)oxide, bis(dibutylacetoxytin)oxide, bis(dioctyllauroyloxytin)oxide, and various combinations of fluorinated alkyl alcohol and raw material ester. Various fluorinated alkyl (meth)acrylates were produced in the same manner as in Example 1 with some changes.
得られた結果を表１に示す、なお、フッ素化アルキルア
ルコールの仕込量を２００ｇとし、仕込モル比をフッ素
化アルキルアルコール：メチル（メタ）アクリレート：
触媒＝ １ ： ４ ： ０．００８とした。The obtained results are shown in Table 1. The amount of fluorinated alkyl alcohol charged was 200 g, and the molar ratio of fluorinated alkyl alcohol: methyl (meth)acrylate:
Catalyst = 1:4:0.008.
（以下余白）
比較例１〜４
触媒種を変える以外は実施例１と同様にしてオクタフル
オロペンチルメタクリレートを製造し、得られた結果を
表２に示す。(The following is a blank space) Comparative Examples 1 to 4 Octafluoropentyl methacrylate was produced in the same manner as in Example 1 except for changing the catalyst species, and the obtained results are shown in Table 2.
［発明の効果］
以上のように、本発明によれば一般式（Ｉ）で示される
有機スズ化合物をエステル交換触媒として用いることに
より高純度のフッ素化アルキル（メタ）アクリレートを
高収率で得ることができる。また、事前の脱水工程や反
応後の洗浄工程の手間が不要で、副反応を引き起こすこ
ともなく、短かい反応時間で目的物を得ることができる
。更には触媒の入手も容易であり、再使用もできること
などから経済的にも大きな効果がある。[Effects of the Invention] As described above, according to the present invention, high purity fluorinated alkyl (meth)acrylate can be obtained in high yield by using the organotin compound represented by general formula (I) as a transesterification catalyst. be able to. Furthermore, there is no need for a preliminary dehydration step or a post-reaction washing step, and the desired product can be obtained in a short reaction time without causing side reactions. Furthermore, the catalyst is easily available and can be reused, so it has great economic effects.
Claims (2)
またはフッ素で、その内少なくとも３個以上がフッ素）
で表わされるフッ素化アルキルアルコールと、メチルア
クリレートまたはメチルメタクリレートとをエステル交
換反応させ、▲数式、化学式、表等があります▼（Ｒは
水素ま たはメチル基）で示されるフッ素化アルキル（メタ）ア
クリレート類を製造するに際し、触媒として一般式（
I ） ▲数式、化学式、表等があります▼（ I ） （Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４はＣ＿４〜Ｃ＿８の
アルキル基、Ｒ＿５はＣ＿１〜Ｃ＿１＿７のアルキル基
）で表わされる有機スズ化合物を用いることを特徴とす
るフッ素化アルキル（メタ）アクリレート類の製造方法
。(1) Y(CX_2)_nCH_2OH (X and Y are hydrogen or fluorine, at least three of which are fluorine)
A fluorinated alkyl (meth)acrylate represented by ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (R is hydrogen or methyl group) by transesterifying a fluorinated alkyl alcohol represented by methyl acrylate or methyl methacrylate. When producing , the general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) Use of an organotin compound represented by (R_1, R_2, R_3, R_4 are C_4 to C_8 alkyl groups, R_5 is C_1 to C_1_7 alkyl groups) Characteristic method for producing fluorinated alkyl (meth)acrylates.
イルオキシスズ）オキサイド、ビス（ジブチルラウロイ
ルオキシスズ）オキサイド、ビス（ジブチルステアロイ
ルオキシスズ）オキサイドからなる群より少なくとも１
種用いる特許請求の範囲第１項記載のフッ素化アルキル
（メタ）アクリレート類の製造方法。(2) At least one organic tin compound selected from the group consisting of bis(dibutyloctanoyloxytin) oxide, bis(dibutyllauroyloxytin) oxide, and bis(dibutylstearoyloxytin) oxide.
A method for producing fluorinated alkyl (meth)acrylates according to claim 1, using a seed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027258A JPS63196544A (en) | 1987-02-10 | 1987-02-10 | Production of fluorinated alkyl (meth)acrylates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027258A JPS63196544A (en) | 1987-02-10 | 1987-02-10 | Production of fluorinated alkyl (meth)acrylates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63196544A true JPS63196544A (en) | 1988-08-15 |
Family
ID=12216052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62027258A Pending JPS63196544A (en) | 1987-02-10 | 1987-02-10 | Production of fluorinated alkyl (meth)acrylates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63196544A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009005A1 (en) * | 1989-12-11 | 1991-06-27 | Smith Kline & French Laboratories Limited | Process |
| US5470969A (en) * | 1990-08-27 | 1995-11-28 | Mcneil-Ppc, Inc. | Catalyzed sucrose-6-ester process |
| CN1054117C (en) * | 1995-01-26 | 2000-07-05 | 中国石化齐鲁石油化工公司 | Method for producing alkyl acrylate or alkyl methacrylate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441814A (en) * | 1977-09-02 | 1979-04-03 | Nitto Chem Ind Co Ltd | Preparation of acrylate or methacrylate |
| JPS59181239A (en) * | 1983-03-30 | 1984-10-15 | Mitsubishi Rayon Co Ltd | Production of fluorine-containing acrylic or methacrylic ester |
-
1987
- 1987-02-10 JP JP62027258A patent/JPS63196544A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441814A (en) * | 1977-09-02 | 1979-04-03 | Nitto Chem Ind Co Ltd | Preparation of acrylate or methacrylate |
| JPS59181239A (en) * | 1983-03-30 | 1984-10-15 | Mitsubishi Rayon Co Ltd | Production of fluorine-containing acrylic or methacrylic ester |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009005A1 (en) * | 1989-12-11 | 1991-06-27 | Smith Kline & French Laboratories Limited | Process |
| US5470969A (en) * | 1990-08-27 | 1995-11-28 | Mcneil-Ppc, Inc. | Catalyzed sucrose-6-ester process |
| CN1054117C (en) * | 1995-01-26 | 2000-07-05 | 中国石化齐鲁石油化工公司 | Method for producing alkyl acrylate or alkyl methacrylate |
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