JP3627223B2 - Method for producing polyfluoroalkyl phosphate - Google Patents

Description

（但し、この一般式中、Ｒは水素原子又は飽和若しくは不飽和結合を含む炭素数１〜１０のアルキル基であり、Ａは単結合又は２価の有機基であり、Ｒｆは直鎖状若しくは分岐鎖状の炭素数１〜２５のポリフルオロアルキル基である。）
で表されるポリフルオロアルキル基含有カルボン酸エステルと、リン酸類とを反応させることを特徴とする、
一般式（ＩＩ）：
（Ｒｆ−Ａ−Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ
（但し、この一般式中、Ｒｆ及びＡは前記したものと同じであり、ｍは１〜３の整数を示す。）
で表されるリン酸ポリフルオロアルキルの製造方法に係るものである。
【０００９】
本発明によれば、容易に入手可能なポリフルオロアルキルハライドから高収率で一般式：ＲＣＯ_２ ＡＲｆなるエステルを製造した後に、リン酸との反応による簡便な方法で、経済的かつ工業的にリン酸ポリフルオロアルキルを製造できるので、効率的な製造が困難であるポリフルオロアルコールを経由する従来法に比べてはるかに優れた製造方法である。
【００１０】
本発明に使用するＲＣＯ_２ ＡＲｆは、例えば、米国特許第３２３９５５７ 号の明細書に記載されるように、ＲｆＣＨ_２ ＣＨ_２ Ｙ（Ｙ＝Ｂｒ又はＩ）で表されるポリフルオロアルキルハライドを無水アルコール溶媒中で

【００１１】
本発明において、原料として使用するポリフルオロアルキル基含有カルボン酸エステルの一般式（Ｉ）において、Ｒｆの炭素数は特に制限がないが、通常は工業的観点から１〜２５が用いられる。また、Ｒは水素原子であってよく、或いは飽和若しくは不飽和結合を含むアルキル基であれば炭素数は特に制限されないが、通常は工業的観点から１〜１０のアルキル基が用いられる。Ｒは、水素原子又は炭素数１〜７のアルキル基が好ましい。
【００１２】

【化２】

が挙げられる。ここで、アンダーラインを付した基は入手性等の点で好ましいものである（以下、同様）。
【００１３】
また、上記一般式（Ｉ）及び（ＩＩ）において、Ａは単結合又は２価の有機基であって、２価の有機基としては、
【化３】

で表される有機基がよい。
【００１４】
こうした２価の有機基において、
【化４】

等が挙げられる。
【００１５】

【化５】

等が挙げられる。
【００１６】
また、
【化６】

等が挙げられる。
【００１７】

【００１８】

【化７】

等が挙げられる。
【００１９】
本発明において使用される代表的なポリフルオロアルキル基含有カルボン酸エステルとしては、例えば、ギ酸エステル、酢酸エステル、プロピオン酸エステル等の飽和カルボン酸エステル類及びアクリル酸エステル、メタクリル酸エステル、クロトン酸エステル等の不飽和カルボン酸エステル類及び
【化８】

等が挙げられるが、その中でも、特に撥水撥油剤の中間体として工業的に大量生産されているポリフルオロアルキル基含有アクリル酸エステルが入手容易という点で好ましい。
【００２０】
本発明で用いられるリン酸類としては、オルトリン酸（Ｈ_３ ＰＯ_４ ）、
【化９】

からなる群より選択されたものであり、その中でも、反応中の粘度を低くするという点でオルトリン酸が好ましい。
【００２１】
本発明の方法によって生成するリン酸ポリフルオロアルキルの例としては、
【化１０】

等が挙げられる。
【００２２】
本発明の反応（広義にはエステル交換反応とも言える。）は、無触媒でも進行するが、触媒を使用する場合は、反応速度を高めるという点で、オルトリン酸（ｐＫａ＝２．１）のｐＫａ以下のｐＫａの酸、例えば、塩酸、硫酸、臭化水素酸、ヨウ化水素酸のような鉱酸、ｐ−トルエンスルホン酸のような有機酸の存在下に行うのが望ましい。その中でも、蒸気圧が低いため、反応中に系外へ除去されにくい硫酸、ｐ−トルエンスルホン酸が特に好ましい。
【００２３】
本発明の反応は不活性溶媒中で行うことも可能であるが、反応容器が大きくなる点及び目的物との分離操作が必要という点から、無溶媒で行うのが反応の効率上好ましい。
【００２４】
生成するカルボン酸（ＲＣＯＯＨ）は反応系外へ順次除去することが望ましいが、この除去方法としては、▲１▼減圧下、▲２▼不活性ガスの流通下、▲３▼酸素を含む気体の流通下、の３つの方法が可能である。
【００２５】
但し、アクリル酸エステルなどの重合性化合物を原料として用いる場合には、上記▲１▼又は▲２▼の方法では、原料のアクリル酸エステル、生成したアクリル酸が重合する可能性があり、これを防止するためにハイドロキノン等の重合禁止剤を使用すると、反応速度が低下するという現象が見られた。
【００２６】
また、たとえ重合禁止剤を用いて系内のアクリル酸エステルの重合を防止できても、生成するアクリル酸を系外へ除去する際、途中でアクリル酸が重合するのを防止することが困難であったが、上記▲３▼の方法を用いた場合は、原料のアクリル酸エステル、生成するアクリル酸の重合を効率よく抑制することが判明し、酸素を含む気体の中でも安全性、経済性の点で空気の流通下で反応を行うのが特に好ましい。
【００２７】
本発明の上記反応の反応温度は５０〜２００ ℃であってよく、特に １００〜１７０ ℃が好ましい。 １００℃より低い場合には、反応に長時間を要するし、 １７０℃を超えると、原料としてアクリル酸エステルなどの重合性化合物を用いる場合は、副反応として重合反応が一部進行する。
【００２８】
また、この反応において、リン酸とポリフルオロアルキル基含有カルボン酸エステルとの割合は、特に制限されないが、通常、後者がリン原子に対して１〜３モルで行われる。
【００２９】
【発明の作用効果】

【００３０】
【実施例】
次に、本発明を実施例について更に具体的に説明するが、この実施例は本発明を何ら限定するものではない。
【００３１】
実施例１
ＣＨ_２ ＝ＣＨＣＯ_２ ＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７ ５１．８ｇ（０．１モル）、８５重量％Ｈ_３ ＰＯ_４ １１．５ｇ（０．１モル）、Ｈ_２ ＳＯ_４ ０．５ｇ（０．００５モル）を、気体導入管、温度計、攪拌機、蒸留塔を装備した ２００ｍｌの４つ口フラスコに入れ、充分に攪拌しつつ乾燥空気を ４００ｍｌ／分で流通させながら １３０℃で２４時間反応を行った。
【００３２】
その後、５ｍｌの水を加え、９０℃で３時間攪拌した後、５０ｍｌの１，２−ジメトキシエタンに溶解し、充分攪拌された１ｌの冷水中に投入して沈澱させた。
【００３３】
沈澱物を濾過後、９０℃で減圧乾燥を行うと、４９．５ｇの褐色の固体が得られた。

【００３４】出発原料及び生成物の同定データは次の通りであった。
【化１１】

【００３５】
【化１２】

【００３６】
副生物としてのＲＣＯＯＨのカルボン酸（ＣＨ_２ ＝ＣＨＣＯＯＨ）は、反応中に流通する乾燥空気により同伴させて、蒸留塔の上部で液化し、受器に溜ることで反応系から除去した。
【００３７】
実施例２
ＣＨ_２ ＝ＣＨＣＯ_２ ＣＨ_２ ＣＨ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＦ_２ ＣＦ_３ （ｎ＝２が ３．１モル％、ｎ＝３が５７．０モル％、ｎ＝４が２７．９モル％、ｎ＝５が ９．３モル％、ｎ＝６が ２．１モル％、ｎ＝７が ０．４モル％、平均分子量：５６９）を５６．９ｇ（０．１モル）使用した以外は実施例１と同様に操作して、褐色固体５４．７ｇを得た。
【００３８】
この化合物の組成は、（ＣＦ_３ ＣＦ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＨ_２ ＣＨ_２ Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が７３．３モル％、ｍ＝２が２６．０モル％、ｍ＝３が ０．７モル％）が９４．６モル％、ＣＦ_３ ＣＦ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＨ_２ ＣＨ_２ ＯＨが ２．６モル％、原料のＣＨ_２ ＝ＣＨＣＯ_２ ＣＨ_２ ＣＨ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＦ_２ ＣＦ_３ が ２．８モル％であった。
【００３９】
実施例３
ＣＨ_３ ＣＯ_２ ＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７を５１．４ｇ（０．１モル）使用した以外は実施例１と同様に操作して、褐色固体５２．８ｇを得た。
【００４０】
この化合物の組成は、（Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が７４．５モル％、ｍ＝２が２４．７モル％、ｍ＝３が ０．８モル％）が９２．３モル％、Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ ＯＨが ４．３モル％、原料のＣＨ_３ ＣＯ_２ ＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７が ３．４モル％であった。
【００４１】
出発原料の分析データは次の通りであった。

【００４２】
実施例４
Ｃ_５ Ｈ_１１ＣＯ_２ ＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７を５６．２ｇ（０．１モル）用い、 １６０℃で２４時間反応を行った以外は実施例１と同様に操作し、褐色固体５１．２ｇを得た。
【００４３】
この化合物の組成は、（Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が７６．５モル％、ｍ＝２が２２．６モル％、ｍ＝３が ０．９モル％）が９３．４モル％、Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ ＯＨが ２．５モル％、原料の Ｃ_５ Ｈ_１１ＣＯ_２ ＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７が ４．１モル％含まれていた。
【００４４】
実施例５
８５重量％Ｈ_３ ＰＯ_４ の代わりに、 １１５重量％ポリリン酸８．５２ｇ（Ｈ_３ ＰＯ_４ として ０．１モル）使用した以外は実施例１と同様に操作し、褐色固体５０．３ｇを得た。
【００４５】
この化合物の組成は、（Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が９２．７モル％、ｍ＝２が ７．３モル％）が９０．３モル％、Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ ＯＨが ２．６モル％、原料のＣＨ_２ ＝ＣＨＣＯＯＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７が ７．１モル％含まれていた。
【００４６】
実施例６
Ｈ_２ ＳＯ_４ の代わりに、ｐ−トルエンスルホン酸を ０．９ｇ（０．００５モル）使用した以外は実施例１と同様に操作し、褐色固体５１．７ｇを得た。
【００４７】
この化合物の組成は、（Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が７５．４モル％、ｍ＝２が２４．０モル％、ｍ＝３が ０．６モル％）が９５．２モル％、Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ ＯＨが ２．４モル％、原料のＣＨ_２ ＝ＣＨＣＯ_２ ＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７が ２．４モル％含まれていた。
【００４８】
実施例７
Ｈ_２ ＳＯ_４ を添加せずに実施例３と同様に操作して、褐色固体３５．０ｇを得た。この化合物の組成は、（Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が５５．１モル％、ｍ＝２が３９．４モル％、ｍ＝３が ５．５モル％）が８６．４モル％、Ｃ_８ Ｆ_１７ＣＨ_２ ＣＨ_２ ＯＨが ０．８モル％、原料のＣＨ_３ ＣＯ_２ ＣＨ_２ ＣＨ_２ Ｃ_８ Ｆ_１７が１２．８モル％含まれていた。
【００４９】
実施例８

【００５０】

【００５１】
出発原料の分析データは次の通りであった。

【００５２】
実施例９

【００５３】

【００５４】
実施例 １０
【化１３】

【００５５】
【化１４】

【００５６】
実施例 １１
実施例２において、ＣＨ_２ ＝ＣＨＣＯ_２ ＣＨ_２ ＣＨ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＦ_２ ＣＦ_３ （ｎ＝２が０．６４モル％、ｎ＝３が ５６．０１モル％、ｎ＝４が ２４．７１モル％、ｎ＝５が １０．５６モル％、ｎ＝６が４．８３モル％、ｎ＝７が１．８７モル％、ｎ＝８が０．８５モル％、ｎ＝９が０．３８モル％、ｎ＝１０が０．１１モル％、平均分子量：５９２）を５９．２ｇ（０．１モル）使用した以外は実施例２と同様に操作して、褐色固体５６．９ｇを得た。
【００５７】
この化合物の組成は、（ＣＦ_３ ＣＦ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＨ_２ ＣＨ_２ Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が７３．３モル％、ｍ＝２が２６．０モル％、ｍ＝３が ０．７モル％）が９４．６モル％、ＣＦ_３ ＣＦ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＨ_２ ＣＨ_２ ＯＨが ２．６モル％、原料のＣＨ_２ ＝ＣＨＣＯ_２ ＣＨ_２ ＣＨ_２ （ＣＦ_２ ＣＦ_２ ）_ｎ ＣＦ_２ ＣＦ_３ が ２．８モル％であった。
【００５８】
比較例１
ＣＨ_３ ＣＯ_２ Ｃ_１２Ｈ_２５を２２．８ｇ（０．１モル）使用した以外は実施例１と同様に操作して、褐色固体２３．２ｇを得た。
【００５９】
この化合物の組成は、（Ｃ_１２Ｈ_２５Ｏ）_ｍ Ｐ（Ｏ）（ＯＨ）_３−ｍ （ｍ＝１が９０．４モル％、ｍ＝２が ９．６モル％）が ９．３モル％、原料のＣＨ_３ ＣＯ_２ Ｃ_１２Ｈ_２５が９０．７モル％含まれていた。[0001]
[Industrial application fields]
The present invention relates to a method for producing a polyfluoroalkyl phosphate useful as a raw material for surface treatment agents such as surfactants, water and oil repellents, mold release agents, and various fluorine-containing derivatives.
[0002]
[Prior art]
Conventionally, as a method for producing polyfluoroalkyl phosphate, for example, a method of reacting polyfluoroalcohol with phosphorus oxyhalide, phosphorus pentoxide or dialkyl phosphite (Japanese Patent Publication No. 48-4770), polyfluoroalcohol and bis A method of hydrolyzing after phosphoryl halide is reacted (Japanese Patent Laid-Open No. 60-64990) is known.
[0003]
However, all of these methods use expensive polyfluoroalcohol as a raw material.
[0004]
As a method for producing a polyfluoroalcohol, there is a method of reacting a polyfluoroalkyl halide with an amide compound and water (Japanese Patent Publication No. 52-8807), but when the amount of water used is too small, the polyfluoroalkyl halide is used. The conversion of decreases.
[0005]
If the reaction conditions are harsh in order to improve this, the production rate of by-product olefins RfCH = CH ₂ resulting from the dehydrohalogenation reaction increases, or if the amount of water used increases, the polyfluoroalkyl halide However, the selectivity of the desired polyfluoroalcohol is reduced. In order to improve the selectivity, there is a two-stage method (Japanese Patent Publication No. 52-17007) in which the polyfluoroalkyl halide is first changed to an ester of RCO ₂ CH ₂ CH ₂ Rf and then changed to a polyfluoroalcohol by hydrolysis reaction. Very large amounts of amide compounds had to be used.
[0006]
[Problems to be solved by the invention]
As described above, since an efficient method for producing polyfluoroalcohol, which is a raw material for producing polyfluoroalkyl phosphate, has not yet been found, economical and industrial phosphoric acid that does not go through polyfluoroalcohol A method for producing polyfluoroalkyl has been desired.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventor generally has a tendency that carboxylic acid esters such as acetates do not easily react with phosphoric acid (see Comparative Example 1 described later). The present inventors completed the present invention by finding that a carboxylic acid ester containing a fluoroalkyl group and phosphoric acid were unexpectedly reacted with extremely high yield to efficiently produce polyfluoroalkyl phosphate.
[0008]
That is, the present invention

(However, in this general formula, R is a hydrogen atom or a C1-C10 alkyl group containing a saturated or unsaturated bond, A is a single bond or a divalent organic group, and Rf is linear or (It is a branched polyfluoroalkyl group having 1 to 25 carbon atoms.)
Characterized by reacting a polyfluoroalkyl group-containing carboxylic acid ester represented by a phosphoric acid,
General formula (II):
(Rf-AO) _m P (O) (OH) _3-m
(However, in this general formula, Rf and A are the same as described above, and m represents an integer of 1 to 3.)
It concerns on the manufacturing method of polyfluoroalkyl phosphate represented by these.
[0009]
According to the present invention, an ester of the general formula: RCO ₂ ARf is produced in a high yield from a readily available polyfluoroalkyl halide, and then economically and industrially by a simple method by reaction with phosphoric acid. Since polyfluoroalkyl phosphate can be produced, the production method is far superior to the conventional method via polyfluoroalcohol, which is difficult to produce efficiently.
[0010]
RCO ₂ ARf used in the present invention is a polyfluoroalkyl halide represented by RfCH ₂ CH ₂ Y (Y = Br or I), for example, as described in the specification of US Pat. No. 3,329,557. In solvent

[0011]
In the present invention, in the general formula (I) of the polyfluoroalkyl group-containing carboxylic acid ester used as a raw material, the carbon number of Rf is not particularly limited, but usually 1 to 25 is used from an industrial viewpoint. R may be a hydrogen atom or the number of carbon atoms is not particularly limited as long as it is an alkyl group containing a saturated or unsaturated bond, but usually an alkyl group of 1 to 10 is used from an industrial viewpoint. R is preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
[0012]

[Chemical formula 2]

Is mentioned. Here, the group with an underline is preferable in terms of availability and the like (hereinafter the same).
[0013]
In the above general formulas (I) and (II), A is a single bond or a divalent organic group.
[Chemical 3]

An organic group represented by
[0014]
In these divalent organic groups,
[Formula 4]

Etc.
[0015]

[Chemical formula 5]

Etc.
[0016]
Also,
[Chemical 6]

Etc.
[0017]

[0018]

[Chemical 7]

Etc.
[0019]
Representative polyfluoroalkyl group-containing carboxylic acid esters used in the present invention include, for example, saturated carboxylic acid esters such as formic acid esters, acetic acid esters, propionic acid esters, acrylic acid esters, methacrylic acid esters, and crotonic acid esters. Unsaturated carboxylic acid esters such as

Among them, polyfluoroalkyl group-containing acrylates that are mass-produced industrially as intermediates for water- and oil-repellents are particularly preferred because they are readily available.
[0020]
Examples of phosphoric acids used in the present invention include orthophosphoric acid (H ₃ PO ₄ ),
[Chemical 9]

Among them, orthophosphoric acid is preferable from the viewpoint of reducing the viscosity during the reaction.
[0021]
Examples of polyfluoroalkyl phosphates produced by the method of the present invention include:
[Chemical Formula 10]

Etc.
[0022]
The reaction of the present invention (also referred to as transesterification in a broad sense) proceeds even without a catalyst, but when a catalyst is used, the pKa of orthophosphoric acid (pKa = 2.1) is increased in that the reaction rate is increased. It is preferable to carry out in the presence of the following pKa acids, for example, mineral acids such as hydrochloric acid, sulfuric acid, hydrobromic acid and hydroiodic acid, and organic acids such as p-toluenesulfonic acid. Of these, sulfuric acid and p-toluenesulfonic acid, which are difficult to remove out of the system during the reaction due to low vapor pressure, are particularly preferred.
[0023]
Although the reaction of the present invention can be carried out in an inert solvent, it is preferably carried out in the absence of a solvent from the viewpoint that the reaction vessel becomes large and a separation operation from the target product is necessary.
[0024]
It is desirable to sequentially remove the carboxylic acid (RCOOH) produced out of the reaction system. This removal method includes (1) reduced pressure, (2) inert gas flow, and (3) oxygen-containing gas. Three methods are possible under distribution.
[0025]
However, when a polymerizable compound such as an acrylic ester is used as a raw material, the raw material acrylic ester and the generated acrylic acid may be polymerized in the method (1) or (2). When a polymerization inhibitor such as hydroquinone was used to prevent this, the reaction rate was decreased.
[0026]
Moreover, even if the polymerization of the acrylic acid ester in the system can be prevented by using a polymerization inhibitor, it is difficult to prevent the acrylic acid from being polymerized in the middle when the generated acrylic acid is removed from the system. However, when the method (3) is used, it has been found that the polymerization of the acrylic ester of the raw material and the generated acrylic acid is efficiently suppressed, and it is safe and economical among gases containing oxygen. It is particularly preferable to carry out the reaction under the air flow.
[0027]
The reaction temperature of the above reaction of the present invention may be 50 to 200 ° C, particularly preferably 100 to 170 ° C. When the temperature is lower than 100 ° C., the reaction takes a long time. When the temperature exceeds 170 ° C., when a polymerizable compound such as an acrylate is used as a raw material, the polymerization reaction partially proceeds as a side reaction.
[0028]
In this reaction, the ratio of phosphoric acid and polyfluoroalkyl group-containing carboxylic acid ester is not particularly limited, but the latter is usually carried out at 1 to 3 moles relative to the phosphorus atom.
[0029]
[Effects of the invention]

[0030]
【Example】
Next, the present invention will be described more specifically with reference to examples. However, the examples do not limit the present invention.
[0031]
Example 1
_{CH 2 = CHCO 2 CH 2 CH} 2 C 8 F 17 51.8g (0.1 mol), 85 _wt% H ₃ PO 4 11.5g (0.1 _{mol), H 2 SO 4 0.5g (} 0. 005 mol) is placed in a 200 ml four-necked flask equipped with a gas inlet tube, thermometer, stirrer, and distillation tower, and the reaction is carried out at 130 ° C. for 24 hours while flowing dry air at 400 ml / min with sufficient stirring. went.
[0032]
Thereafter, 5 ml of water was added, and the mixture was stirred at 90 ° C. for 3 hours, dissolved in 50 ml of 1,2-dimethoxyethane, and poured into 1 liter of sufficiently stirred cold water to cause precipitation.
[0033]
The precipitate was filtered and dried under reduced pressure at 90 ° C. to obtain 49.5 g of a brown solid.

The starting material and product identification data were as follows:
Embedded image

[0035]
Embedded image

[0036]
RCOOH carboxylic acid (CH ₂ ═CHCOOH) as a by-product was entrained by dry air flowing during the reaction, liquefied in the upper part of the distillation column, and removed from the reaction system by collecting in the receiver.
[0037]
Example 2
_{CH 2 = CHCO 2 CH 2 CH} 2 (CF 2 CF 2) n CF 2 CF 3 (n = 2 is 3.1 mol%, n = 3 57.0 mol%, n = 4 27.9 mol% N = 5 is 9.3 mol%, n = 6 is 2.1 mol%, n = 7 is 0.4 mol%, and the average molecular weight is 56.9). The same operation as in Example 1 was performed to obtain 54.7 g of a brown solid.
[0038]
The composition of this _{compound, (CF 3 CF 2 (CF} 2 CF 2) n CH 2 CH 2 O) m P (O) (OH) 3-m (m = 1 is 73.3 mol%, m = 2 is 26.0 mole%, m = 3 is 0.7 mol%) 94.6 _{mol%, CF 3 CF 2 (CF} 2 CF 2) n CH 2 CH 2 OH is 2.6 mol%, the raw material of the CH _{2 = CHCO 2 CH 2 CH 2 (} CF 2 CF 2) n CF 2 CF 3 was 2.8 mol%.
[0039]
Example 3
The same operation as in Example 1 was carried out except that 51.4 g (0.1 mol) of CH ₃ CO ₂ CH ₂ CH ₂ C ₈ F ₁₇ was used, to obtain 52.8 g of a brown solid.
[0040]
The composition of this _{compound, (C 8 F 17 CH 2} CH 2 O) m P (O) (OH) 3-m (m = 1 is 74.5 mol%, m = 2 is 24.7 mol%, m = 3 0.8 mol%) is 92.3 _{mol%, C 8 F 17 CH 2} CH 2 OH is 4.3 mol%, the raw material of the _{CH 3 CO 2 CH 2 CH 2} C 8 F 17 3.4 Mol%.
[0041]
The analytical data of the starting material was as follows.

[0042]
Example 4
The same procedure was followed as in Example 1 except that 56.2 g (0.1 mol) of C ₅ H ₁₁ CO ₂ CH ₂ CH ₂ C ₈ F ₁₇ was used and the reaction was carried out at 160 ° C. for 24 hours. 2 g was obtained.
[0043]
The composition of this _{compound, (C 8 F 17 CH 2} CH 2 O) m P (O) (OH) 3-m (m = 1 is 76.5 mol%, m = 2 is 22.6 mol%, m = 3 0.9 mol%) 93.4 _{mol%, C 8 F 17 CH 2} CH 2 OH is 2.5 mol%, the raw material of _{C 5 H 11 CO 2 CH 2} CH 2 C 8 F 17 4 Contained 1 mol%.
[0044]
Example 5
Instead of 85 _wt% H 3 PO _{4, (0.1} mol as H 3 PO ₄₎ 115 wt% polyphosphoric acid 8.52g except that used were the same manner as in Example 1 to give a brown solid 50.3g It was.
[0045]
The composition of this compound _{is (C 8 F 17 CH 2 CH} 2 O) m P (O) (OH) 3-m (m = 1 is 92.7 mol%, m = 2 is 7.3 mol%) 90.3 _mol%, 2.6 mol% _{C 8 F 17 CH 2 CH 2} OH, raw material of _{CH 2 = CHCOOCH 2 CH 2 C} 8 F 17 was contained 7.1 mol%.
[0046]
Example 6
The same operation as in Example 1 was carried out except that 0.9 g (0.005 mol) of p-toluenesulfonic acid was used instead of H ₂ SO ₄ to obtain 51.7 g of a brown solid.
[0047]
The composition of this _{compound, (C 8 F 17 CH 2} CH 2 O) m P (O) (OH) 3-m (m = 1 is 75.4 mol%, m = 2 is 24.0 mol%, m = 3 0.6 mol%) is 95.2 _{mol%, C 8 F 17 CH 2} CH 2 OH is 2.4 mol%, the raw material of _{CH 2 = CHCO 2 CH 2 CH} 2 C 8 F 17 is 2. 4 mol% was contained.
[0048]
Example 7
The same operation as in Example 3 was carried out without adding H ₂ SO ₄ to obtain 35.0 g of a brown solid. The composition of this _{compound, (C 8 F 17 CH 2} CH 2 O) m P (O) (OH) 3-m (m = 1 is 55.1 mol%, m = 2 is 39.4 mol%, m = 3 5.5 mol%) is 86.4 _{mol%, C 8 F 17 CH 2} CH 2 OH 0.8 mol%, the raw material of the _{CH 3 CO 2 CH 2 CH 2} C 8 F 17 12.8 Mole% was included.
[0049]
Example 8

[0050]

[0051]
The analytical data of the starting material was as follows.

[0052]
Example 9

[0053]

[0054]
Example 10
Embedded image

[0055]
Embedded image

[0056]
Example 11
In Example _{2, CH 2 = CHCO 2 CH} 2 CH 2 (CF 2 CF 2) n CF 2 CF 3 (n = 2 0.64 mol%, n = 3 is 56.01 mol%, n = 4 is 24.71 mol%, n = 5 is 10.56 mol%, n = 6 is 4.83 mol%, n = 7 is 1.87 mol%, n = 8 is 0.85 mol%, n = 9 is 0.39 mol%, n = 10 was 0.11 mol%, average molecular weight: 592) was used in the same manner as in Example 2 except that 59.2 g (0.1 mol) was used, and 56.9 g of a brown solid. Got.
[0057]
The composition of this _{compound, (CF 3 CF 2 (CF} 2 CF 2) n CH 2 CH 2 O) m P (O) (OH) 3-m (m = 1 is 73.3 mol%, m = 2 is 26.0 mole%, m = 3 is 0.7 mol%) 94.6 _{mol%, CF 3 CF 2 (CF} 2 CF 2) n CH 2 CH 2 OH is 2.6 mol%, the raw material of the CH _{2 = CHCO 2 CH 2 CH 2 (} CF 2 CF 2) n CF 2 CF 3 was 2.8 mol%.
[0058]
Comparative Example 1
The same operation as in Example 1 was carried out except that 22.8 g (0.1 mol) of CH ₃ CO ₂ C ₁₂ H ₂₅ was used to obtain 23.2 g of a brown solid.
[0059]
The composition of this compound _{is (C 12 H 25 O) m} P (O) (OH) 3-m (m = 1 is 90.4 mol%, m = 2 is 9.6 mol%) 9.3 mole %, And 90.7 mol% of the raw material CH ₃ CO ₂ C ₁₂ H ₂₅ was contained.

Claims (10)

Formula (I):

(However, in this general formula, R is a hydrogen atom or a C1-C10 alkyl group containing a saturated or unsaturated bond, A is a single bond or a divalent organic group, and Rf is linear or (It is a branched polyfluoroalkyl group having 1 to 25 carbon atoms.)
Characterized by reacting a polyfluoroalkyl group-containing carboxylic acid ester represented by a phosphoric acid,
General formula (II):
(Rf-AO) _m P (O) (OH) _3-m
(However, in this general formula, Rf and A are the same as described above, and m represents an integer of 1 to 3.)
The manufacturing method of polyfluoroalkyl phosphate represented by these. The manufacturing method of Claim 1 whose R is a C1-C7 alkyl group containing a hydrogen atom or a saturated or unsaturated bond. The manufacturing method of Claim 1 or 2 whose A is a single bond. A is a single bond or a divalent organic group. As the divalent organic group,

The manufacturing method according to claim 1 or 2, wherein The production method according to any one of claims 1 to 4, wherein the reaction is carried out in the presence of an acid having a pKa of 2.1 or less. The production method according to claim 5, wherein the acid having a pKa of 2.1 or less is sulfuric acid or p-toluenesulfonic acid. The production method according to claim 2, wherein the reaction is performed under a flow of a gas containing oxygen. The manufacturing method according to any one of claims 1 to 7, wherein the phosphoric acid is selected from the group consisting of orthophosphoric acid, polyphosphoric acid and metaphosphoric acid.

The manufacturing method of any one of Claims 1-8 removed out of a reaction system. The manufacturing method of any one of Claims 1-9 which performs reaction at 100-170 degreeC.