JP2010215518A - Polyfluoroalkylphosphonic acid and method for producing the same - Google Patents
Polyfluoroalkylphosphonic acid and method for producing the same Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 150000005690 diesters Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 2
- 150000001875 compounds Chemical group 0.000 abstract description 40
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 231100000693 bioaccumulation Toxicity 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 35
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 150000002978 peroxides Chemical class 0.000 description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 6
- -1 diisopropyl Secondary butyl peroxydicarbonate Chemical group 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 5
- 238000001577 simple distillation Methods 0.000 description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 239000006082 mold release agent Substances 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical group C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical group CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical class OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical group CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical group CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Description
本発明は、ポリフルオロアルキルホスホン酸およびその製造法に関する。さらに詳しくは、離型剤の有効成分等として用いられるポリフルオロアルキルホスホン酸およびその製造法に関する。 The present invention relates to a polyfluoroalkylphosphonic acid and a method for producing the same. More specifically, the present invention relates to a polyfluoroalkylphosphonic acid used as an active ingredient of a release agent and a method for producing the same.
ポリフルオロアルキルホスホン酸エステルは、離型剤の合成原料として広く用いられている。離型剤としたときの離型性能は、パーフルオロアルキル基の炭素数が8〜12である化合物において最も発現し易く、特にC8のテロマー化合物である
CF3(CF2)7CH2CH2P(O)(OC2H5)2
が、この種の用途に好んで使用されている(特許文献１〜４参照)。
Polyfluoroalkylphosphonic acid esters are widely used as raw materials for synthesizing release agents. The mold release performance when used as a mold release agent is most easily manifested in compounds having 8 to 12 carbon atoms in the perfluoroalkyl group, and is particularly a C 8 telomer compound.
CF 3 (CF 2 ) 7 CH 2 CH 2 P (O) (OC 2 H 5 ) 2
However, it is preferably used for this kind of application (see Patent Documents 1 to 4).
ところで、炭素数8〜12のパーフルオロアルキル基を有するテロマー化合物は、環境中で生物分解されて、生体蓄積性、環境濃縮性が比較的高い化合物に変化することが報告されており、処理工程での暴露、廃棄物、処理基材等からの環境への放出、拡散などが懸念されている。また、パーフルオロアルキル基の炭素数が14以上の化合物では、それの物理的、化学的性状からそれの取扱いが非常に困難であり、実際には殆ど使用されていない。 By the way, it has been reported that a telomer compound having a perfluoroalkyl group having 8 to 12 carbon atoms is biodegraded in the environment and converted into a compound having a relatively high bioaccumulation property and environmental concentration property. There are concerns about exposure to the environment, waste, release to the environment from treated substrates, and diffusion. In addition, compounds having a perfluoroalkyl group with 14 or more carbon atoms are very difficult to handle because of their physical and chemical properties, and are rarely used in practice.
さらに、炭素数8以上のパーフルオロアルキル基を有するテロマー化合物は、その製造プロセスにおいて、生体蓄積性の高いパーフルオロオクタン酸類の発生や混入が避けられない。そのため、このようなテロマー化合物の製造各社は、それの製造からの撤退や炭素数6以下のパーフルオロアルキル基を有する化合物への代替などを進めている。 Furthermore, telomer compounds having a perfluoroalkyl group having 8 or more carbon atoms cannot avoid the generation or contamination of perfluorooctanoic acids having high bioaccumulation potential in the production process. For this reason, manufacturers of such telomer compounds are proceeding withdrawing from the production or replacing them with compounds having a perfluoroalkyl group having 6 or less carbon atoms.
しかしながら、パーフルオロアルキル基の炭素数が6以下の化合物では、処理基材表面での配向性が著しく低下し、また融点、ガラス転移点Tgなどが炭素数8の化合物に比べて著しく低いため、温度、湿度、応力、有機溶剤の接触などの使用環境条件に大きな影響を受けることとなる。そのため、求められる十分な性能が得られず、また耐久性などにも影響がみられる。 However, in the compound having 6 or less carbon atoms in the perfluoroalkyl group, the orientation on the surface of the treated substrate is remarkably lowered, and the melting point, glass transition point Tg, etc. are remarkably lower than those in the compound having 8 carbon atoms. It will be greatly affected by environmental conditions such as temperature, humidity, stress, and contact with organic solvents. Therefore, the required sufficient performance cannot be obtained, and the durability is also affected.
本発明の目的は、生体蓄積性が低いといわれる炭素数6以下のパーフルオロアルキル基を有する化合物であって、離型剤の合成原料等として有効に使用し得るポリフルオロアルキルホスホン酸およびその製造法を提供することにある。 An object of the present invention is a compound having a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation potential, and can be used effectively as a raw material for synthesizing a mold release agent, and its production To provide a law.
本発明によって、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2 〔I〕
(ここで、nは1〜6の整数、aは1〜4の整数、bは1〜3の整数、cは1〜3の整数である)で表わされるポリフルオロアルキルホスホン酸が提供される。
According to the invention, the general formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OH) 2 (I)
(Where n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3). .
かかるポリフルオロアルキルホスホン酸は、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OR)2 〔II〕
(ここで、Rは炭素数1〜4のアルキル基であり、nは1〜6の整数、aは1〜4の整数、bは1〜3の整数、cは1〜3の整数である)で表わされるポリフルオロアルキルホスホン酸ジエステルを加水分解反応させることによって製造される。
Such polyfluoroalkylphosphonic acids have the general formula
C n F 2n + 1 (CH 2 CF 2) a (CF 2 CF 2) b (CH 2 CH 2) c P (O) (OR) 2 (II)
(Where R is an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3) ) Represented by a hydrolysis reaction.
本発明に係るポリフルオロアルキルホスホン酸は、環境中へ放出されたとき、分子中の-CH2CF2-結合部分で脱HF化されて二重結合が形成され、それがオゾン分解などされて、環境濃縮性、生体蓄積性などの低い化合物へ分解され易い構造を有するようになり、またその製造過程でパーフルオロアルキルカルボン酸等の環境負荷物質を生成させない。しかも、従来用いられていた化合物と同様に、離型剤の合成原料等として有効に使用することができる。 When the polyfluoroalkylphosphonic acid according to the present invention is released into the environment, it is deHFed at the —CH 2 CF 2 — bonding moiety in the molecule to form a double bond, which is subjected to ozonolysis and the like. In addition, it has a structure that is easily decomposed into a compound having a low environmental concentration and a low bioaccumulation property, and does not generate an environmental load substance such as perfluoroalkylcarboxylic acid in the production process. Moreover, it can be used effectively as a raw material for synthesizing mold release agents, as in the case of conventionally used compounds.
本発明に係るポリフルオロアルキルホスホン酸〔I〕は、ポリフルオロアルキルホスホン酸ジエステル〔II〕を加水分解反応させることにより得ることができる。この反応の原料物質として用いられるポリフルオロアルキルホスホン酸ジエステル〔II〕は、ポリフルオロアルキルアイオダイド〔III〕
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cI 〔III〕
とトリアルキルホスファイトP(OR)3を反応させることにより得られる。ポリフルオロアルキルアイオダイド〔III〕は、公知の化合物であり、特許文献５に記載されている。
The polyfluoroalkylphosphonic acid [I] according to the present invention can be obtained by hydrolyzing the polyfluoroalkylphosphonic acid diester [II]. The polyfluoroalkylphosphonic acid diester [II] used as a raw material for this reaction is a polyfluoroalkyl iodide [III].
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c I (III)
And trialkyl phosphite P (OR) 3 . Polyfluoroalkyl iodide [III] is a known compound and is described in Patent Document 5.
ポリフルオロアルキルホスホン酸ジエステル〔II〕合成の出発原料となるポリフルオロアルキルアイオダイド〔III〕は、一般式
CnF2n+1(CH2CF2)a(CF2CF2)bI 〔IV〕
で表わされる末端ヨウ素化化合物にエチレンを付加反応させることにより製造される。エチレンの付加反応は、上記化合物〔IV〕に過酸化物開始剤の存在下で加圧エチレンを付加反応させることにより行われ、その付加数は反応条件にもよるが、1〜3、好ましくは1である。なお、反応温度は用いられる開始剤の分解温度にも関係するが、反応は一般に約80〜120℃で行われ、低温で分解する過酸化物開始剤を用いた場合には80℃以下での反応が可能である。
Polyfluoroalkyl iodide [III] as a starting material for the synthesis of polyfluoroalkylphosphonic acid diester [II]
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b I (IV)
It is produced by addition reaction of ethylene with a terminal iodinated compound represented by the formula: The addition reaction of ethylene is carried out by subjecting the above compound [IV] to an addition reaction of pressurized ethylene in the presence of a peroxide initiator, and the number of addition depends on the reaction conditions, but is preferably 1 to 3, preferably 1. Although the reaction temperature is related to the decomposition temperature of the initiator used, the reaction is generally performed at about 80 to 120 ° C., and when a peroxide initiator that decomposes at a low temperature is used, the reaction temperature is 80 ° C. or less. Reaction is possible.
過酸化物開始剤としては、第3ブチルパーオキサイド、ジ(第3ブチルシクロヘキシル)パーオキシジカーボネート、ジセチルパーオキシジカーボネート、ジ-n-プロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジ第2ブチルパーオキシジカーボネート等が、反応の進歩性および制御性の点から、上記化合物〔IV〕に対して約1〜5モル％の割合で用いられる。 Peroxide initiators include tertiary butyl peroxide, di (tertiary butyl cyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, diisopropyl Secondary butyl peroxydicarbonate or the like is used at a ratio of about 1 to 5 mol% with respect to the above compound [IV] in terms of the inventive step and controllability of the reaction.
なお、前記末端ヨウ素化化合物〔IV〕は、次のような一連の工程を経て合成される。
(1)一般式
CnF2n+1I (n：1〜6)
で表わされるパーフルオロアルキルアイオダイドを、上記の如き過酸化物開始剤(原料化合物に対し約0.1〜0.5モル％の使用量)の存在下でフッ化ビニリデンと反応させ、一般式
CnF2n+1(CH2CF2)aI 〔V〕
で表わされる化合物を得る。
(2)上記一般式〔V〕で表わされる化合物に、過酸化物開始剤の存在下でテトラフルオロエチレンを反応させることにより、前記一般式〔IV〕で表わされる末端ヨウ素化化合物が得られる。この一般式〔IV〕において、bは1〜3、好ましくは1〜2の整数である。この反応に用いられる過酸化物開始剤としては、前記の如き有機過酸化物開始剤が(1)と同様の割合で用いられる。
The terminal iodinated compound [IV] is synthesized through the following series of steps.
(1) General formula
C n F 2n + 1 I (n: 1-6)
Is reacted with vinylidene fluoride in the presence of a peroxide initiator as described above (amount used in an amount of about 0.1 to 0.5 mol% based on the raw material compound),
C n F 2n + 1 (CH 2 CF 2 ) a I (V)
To obtain a compound represented by:
(2) By reacting the compound represented by the general formula [V] with tetrafluoroethylene in the presence of a peroxide initiator, the terminal iodinated compound represented by the general formula [IV] is obtained. In the general formula [IV], b is an integer of 1 to 3, preferably 1 to 2. As the peroxide initiator used in this reaction, the organic peroxide initiator as described above is used in the same proportion as (1).
フッ化ビニリデンおよびテトラフルオロエチレン付加反応の反応温度は、用いられる開始剤の分解温度にも依存するが、低温で分解する過酸化物開始剤を用いることにより、低圧条件下でも80℃以下での反応が可能である。反応は、CnF2n+1Iまたは前記化合物〔V〕をオートクレーブ内に入れ、その内温を昇温させて約10〜60℃、例えば50℃としたら、そこにCnF2n+1Iまたは化合物〔V〕に溶解した過酸化物系開始剤を加え、内温が例えば55℃になったら、フッ化ビニリデンまたはテトラフルオロエチレンを約0.1〜0.6MPaの圧力を保ちながら分添し、所望量を分添した後、例えば約55〜80℃の間の温度で約1時間程度エージングすることにより行われる。その添加量によって、反応によって付加したフッ化ビニリデンまたはテトラフルオロエチレン骨格の数aまたはbが左右される。一般には、種々のa値およびb値の混合物として形成される。 The reaction temperature of vinylidene fluoride and tetrafluoroethylene addition reaction also depends on the decomposition temperature of the initiator used, but by using a peroxide initiator that decomposes at low temperatures, Reaction is possible. In the reaction, when C n F 2n + 1 I or the compound [V] is put in an autoclave and the internal temperature is raised to about 10-60 ° C., for example, 50 ° C., C n F 2n + 1 is added thereto. Peroxide-based initiator dissolved in I or compound [V] is added, and when the internal temperature reaches 55 ° C., for example, vinylidene fluoride or tetrafluoroethylene is added while maintaining a pressure of about 0.1 to 0.6 MPa, After the desired amount is dispensed, it is carried out, for example, by aging at a temperature of about 55 to 80 ° C. for about 1 hour. The number a or b of vinylidene fluoride or tetrafluoroethylene skeleton added by the reaction depends on the amount added. Generally, it is formed as a mixture of various a and b values.
これらの反応が、低温で反応を行えるということは、エネルギーの使用量を減少させることが可能となるばかりではなく、設備内でのフッ酸等による腐食を抑制し、設備の更新頻度を減らすことができる。さらに、より廉価な材料の使用が可能となることから、更新頻度の減少と併せて、設備投資費用を廉価に抑えることができる。 The fact that these reactions can be carried out at low temperatures not only makes it possible to reduce the amount of energy used, but also suppresses corrosion due to hydrofluoric acid in the equipment and reduces the frequency of equipment renewal. Can do. Furthermore, since it is possible to use a cheaper material, it is possible to keep down the capital investment cost at a low price together with a decrease in the renewal frequency.
エチレンが付加される具体的な化合物〔IV〕としては、次のような化合物が例示される。これらの化合物は、種々のa値およびb値を有するオリゴマーの混合物であり、特定のa値およびb値を有するオリゴマーは混合物を蒸留することにより単離することができる。なお、所定のa値およびb値を有しないオリゴマーは、それを単離してまたは混合物のまま、再度フッ化ビニリデンまたはテトラフルオロエチレンとのオリゴマー数増加反応に用いることができる。
C2F5(CH2CF2)(CF2CF2)I
C2F5(CH2CF2)(CF2CF2)2I
C2F5(CH2CF2)2(CF2CF2)I
C2F5(CH2CF2)2(CF2CF2)2I
C4F9(CH2CF2)(CF2CF2)I
C4F9(CH2CF2)2(CF2CF2)I
C4F9(CH2CF2)(CF2CF2)2I
C4F9(CH2CF2)2(CF2CF2)2I
C2F5(CH2CF2)(CF2CF2)3I
C4F9(CH2CF2)(CF2CF2)3I
Specific compounds [IV] to which ethylene is added include the following compounds. These compounds are mixtures of oligomers having various a and b values, and oligomers having specific a and b values can be isolated by distilling the mixture. In addition, the oligomer which does not have predetermined | prescribed a value and b value can be used again for the oligomer number increase reaction with vinylidene fluoride or tetrafluoroethylene, isolating it or with a mixture.
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) I
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I
C 2 F 5 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) I
C 2 F 5 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) I
C 4 F 9 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) I
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I
C 4 F 9 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) 2 I
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 3 I
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 3 I
上記例示された如き化合物〔IV〕に、エチレンを付加反応させたポリフルオロアルキルアイオダイド〔III〕には、トリアルキルホスファイト、例えばトリメチルホスファイト、トリエチルホスファイト、トリプロピルホスファイト、トリブチルホスファイト等の炭素数1〜4のアルキル基を有するトリアルキルホスファイトP(OR)3を反応させ、脱RI化反応させることにより、原料物質たるポリフルオロアルキルホスホン酸ジエステル〔II〕を得ることができる。なお、化合物〔IV〕にエチレンを付加反応させないと、トリアルキルホスファイトとの脱RI化反応が進行しない。 Polyfluoroalkyl iodides [III] obtained by addition reaction of ethylene with compounds [IV] as exemplified above include trialkyl phosphites such as trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite. The polyfluoroalkylphosphonic acid diester [II] as a raw material can be obtained by reacting a trialkyl phosphite P (OR) 3 having a C 1-4 alkyl group such as . In addition, unless the compound [IV] is subjected to an addition reaction with ethylene, the deRI reaction with the trialkyl phosphite does not proceed.
ポリフルオロアルキルホスホン酸ジエステル〔II〕の加水分解反応は、濃塩酸によって代表される無機酸等の酸性触媒の存在下で約90〜100℃で攪拌することにより容易に行われる。反応混合物は、減圧ロ過された後、水洗・ロ過、アセトン洗浄・ロ過する方法などにより、目的物たるポリフルオロアルキルホスホン酸〔I〕を90％台の好収率で得ることができる。 The hydrolysis reaction of the polyfluoroalkylphosphonic acid diester [II] is easily performed by stirring at about 90 to 100 ° C. in the presence of an acidic catalyst such as an inorganic acid typified by concentrated hydrochloric acid. After the reaction mixture is filtered under reduced pressure, the target product polyfluoroalkylphosphonic acid [I] can be obtained in a good yield of 90% by a method such as washing with water, filtration, washing with acetone and filtration. .
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
参考例１
温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)I (99GC％)
500g(0.78モル)およびトリエチルホスファイトP(OC2H5)3 181g(1.56モル)を仕込み、155℃で攪拌した。このとき、副生生物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に91g(0.78モル)宛4回分添し、合計18時間攪拌した。
Reference example 1
In a 1 L four-necked flask equipped with a thermometer and a low-boiler removal receiver,
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) I (99GC%)
500 g (0.78 mol) and triethyl phosphite P (OC 2 H 5 ) 3 181 g (1.56 mol) were charged and stirred at 155 ° C. At this time, in order to remove ethyl iodide as a by-product from the reaction system, nitrogen gas was bubbled into the reaction solution using a thin tube. A small amount of the reaction solution was collected and analyzed by gas chromatography. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added four times to 91 g (0.78 mol) at a time and stirred for a total of 18 hours. .
反応終了後、反応混合物を内圧0.2kPa、内温160〜170℃、塔頂温度150〜155℃の条件下で減圧単蒸留を行い、蒸留留分を水洗して、精製反応生成物(96GC％)412g(収率78％)を得た。 After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C., and a tower top temperature of 150 to 155 ° C., and the distillation fraction was washed with water to obtain a purified reaction product (96 GC% ) 412 g (yield 78%) was obtained.
得られた精製反応生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる化合物であることが確認された。
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2
1H-NMR(CD3OD、TMS)：δ3.37(CH 2CF2)
2.42(CH 2CH2)
2.07(CH2CH 2)
4.13(CH 2CH3)
1.36(CH2CH 3)
19F-NMR(CD3OD、C6F6):ppm -80.2(CF 3)
-124.6(CF3CF 2CF2CF2)
-122.3(CF3CF2CF 2CF2)
-110.0(CF 2CH2CF2)
-110.0(CF2CH2CF 2)
-120.0(CH2CF2CF 2CF2)
-121.6(CH2CF2CF2CF 2)
-122.1(CF 2CF2CH2CH2)
-113.8(CF2CF 2CH2CH2)
The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
1 H-NMR (CD 3 OD, TMS): δ 3.37 (C H 2 CF 2 )
2.42 (C H 2 CH 2 )
2.07 (CH 2 C H 2 )
4.13 (C H 2 CH 3 )
1.36 (CH 2 C H 3 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -80.2 (C F 3 )
-124.6 (CF 3 C F 2 CF 2 CF 2 )
-122.3 (CF 3 CF 2 C F 2 CF 2 )
-110.0 (C F 2 CH 2 CF 2 )
-110.0 (CF 2 CH 2 C F 2 )
-120.0 (CH 2 CF 2 C F 2 CF 2 )
-121.6 (CH 2 CF 2 CF 2 C F 2 )
-122.1 (C F 2 CF 2 CH 2 CH 2 )
-113.8 (CF 2 C F 2 CH 2 CH 2 )
参考例２
温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)I (99GC％)
500g(0.92モル)およびトリエチルホスファイトP(OC2H5)3 213g(1.84モル)を仕込み、155℃で攪拌した。このとき、副生生物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に107g(0.92モル)宛4回分添し、合計18時間攪拌した。
Reference example 2
In a 1 L four-necked flask equipped with a thermometer and a low-boiler removal receiver,
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I (99GC%)
500 g (0.92 mol) and triethyl phosphite P (OC 2 H 5 ) 3 213 g (1.84 mol) were charged and stirred at 155 ° C. At this time, in order to remove ethyl iodide as a by-product from the reaction system, nitrogen gas was bubbled into the reaction solution using a thin tube. A small amount of the reaction solution was collected and subjected to gas chromatography analysis. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added 4 times to 107 g (0.92 mol) at a time and stirred for a total of 18 hours. .
反応終了後、反応混合物を内圧0.2kPa、内温145〜155℃、塔頂温度138〜142℃の条件下で減圧単蒸留を行い、蒸留留分を水洗して、精製反応生成物(98GC％)407g(収率79％)を得た。 After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 145 to 155 ° C., and a tower top temperature of 138 to 142 ° C., and the distillation fraction was washed with water to give a purified reaction product (98 GC% 407 g (79% yield) was obtained.
得られた精製反応生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる化合物であることが確認された。
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2
1H-NMR(CD3OD、TMS)：δ3.37(CH 2CF2)
2.43(CH 2CH2)
2.07(CH2CH 2)
4.13(CH 2CH3)
1.36(CH2CH 3)
19F-NMR(CD3OD、C6F6):ppm -80.2(CF 3)
-124.0(CF3CF 2CF2CF2)
-122.3(CF3CF2CF 2CF2)
-110.3(CF 2CH2CF2)
-109.8(CF2CH2CF 2)
-124.4(CH2CF2CF 2CF2)
-113.1(CH2CF2CF2CF 2)
The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
1 H-NMR (CD 3 OD, TMS): δ 3.37 (C H 2 CF 2 )
2.43 (C H 2 CH 2 )
2.07 (CH 2 C H 2 )
4.13 (C H 2 CH 3 )
1.36 (CH 2 C H 3 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -80.2 (C F 3 )
-124.0 (CF 3 C F 2 CF 2 CF 2 )
-122.3 (CF 3 CF 2 C F 2 CF 2 )
-110.3 (C F 2 CH 2 CF 2 )
-109.8 (CF 2 CH 2 C F 2 )
-124.4 (CH 2 CF 2 C F 2 CF 2 )
-113.1 (CH 2 CF 2 CF 2 C F 2 )
参考例３
温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)I (97GC％)
500g(0.76モル)およびトリエチルホスファイトP(OC2H5)3 176g(1.52モル)を仕込み、155℃で攪拌した。このとき、副生生物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に88g(0.76モル)宛4回分添し、合計18時間攪拌した。
Reference example 3
In a 1 L four-necked flask equipped with a thermometer and a low-boiler removal receiver,
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) I (97GC%)
500 g (0.76 mol) and triethyl phosphite P (OC 2 H 5 ) 3 176 g (1.52 mol) were charged and stirred at 155 ° C. At this time, in order to remove ethyl iodide as a by-product from the reaction system, nitrogen gas was bubbled into the reaction solution using a thin tube. A small amount of the reaction solution was collected and subjected to gas chromatography analysis. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added to 88 g (0.76 mol) at a time, and stirred for a total of 18 hours. .
反応終了後、反応混合物を内圧0.2kPa、内温160〜170℃、塔頂温度150〜155℃の条件下で減圧単蒸留を行い、蒸留留分を水洗して、精製反応生成物(96GC％)395g(収率77％)を得た。 After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C., and a tower top temperature of 150 to 155 ° C., and the distillation fraction was washed with water to obtain a purified reaction product (96 GC% ) 395 g (yield 77%) was obtained.
得られた精製反応生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる化合物であることが確認された。
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OCH2CH3)2
1H-NMR(CD3OD、TMS)：δ3.34(CH 2CF2)
2.42(CH 2CH2)
2.07(CH2CH 2)
4.13(CH 2CH3)
1.36(CH2CH 3)
19F-NMR(CD3OD、C6F6):ppm -85.3(CF 3)
-114.0(CF3CF 2CH2CF2)
-110.2(CH2CF 2CF2CF2CF2CF2CF2CF2)
-120.0(CH2CF2CF 2CF2CF2CF2CF2CF2)
-119.5(CH2CF2CF2CF 2CF2CF2CF2CF2)
-120.3(CH2CF2CF2CF2CF 2CF2CF2CF2)
-121.4(CH2CF2CF2CF2CF2CF 2CF2CF2)
-122.0(CH2CF2CF2CF2CF2CF2CF 2CF2)
-114.8(CH2CF2CF2CF2CF2CF2CF2CF 2)
The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
1 H-NMR (CD 3 OD, TMS): δ 3.34 (C H 2 CF 2 )
2.42 (C H 2 CH 2 )
2.07 (CH 2 C H 2 )
4.13 (C H 2 CH 3 )
1.36 (CH 2 C H 3 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -85.3 (C F 3 )
-114.0 (CF 3 C F 2 CH 2 CF 2 )
-110.2 (CH 2 C F 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )
-120.0 (CH 2 CF 2 C F 2 CF 2 CF 2 CF 2 CF 2 CF 2 )
-119.5 (CH 2 CF 2 CF 2 C F 2 CF 2 CF 2 CF 2 CF 2 )
-120.3 (CH 2 CF 2 CF 2 CF 2 C F 2 CF 2 CF 2 CF 2 )
-121.4 (CH 2 CF 2 CF 2 CF 2 CF 2 C F 2 CF 2 CF 2 )
-122.0 (CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 C F 2 CF 2 )
-114.8 (CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 C F 2 )
参考例４
温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)I (97GC％)
500g(0.90モル)およびトリエチルホスファイトP(OC2H5)3 208g(1.80モル)を仕込み、155℃で攪拌した。このとき、副生生物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に104g(0.90モル)宛4回分添し、合計18時間攪拌した。
Reference example 4
In a 1 L four-necked flask equipped with a thermometer and a low-boiler removal receiver,
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) I (97GC%)
500 g (0.90 mol) and triethyl phosphite P (OC 2 H 5 ) 3 208 g (1.80 mol) were charged and stirred at 155 ° C. At this time, in order to remove ethyl iodide as a by-product from the reaction system, nitrogen gas was bubbled into the reaction solution using a thin tube. A small amount of the reaction solution was collected and analyzed by gas chromatography. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added 4 times to 104 g (0.90 mol) at a time and stirred for a total of 18 hours. .
反応終了後、反応混合物を内圧0.2kPa、内温145〜155℃、塔頂温度138〜141℃の条件下で減圧単蒸留を行い、蒸留留分を水洗して、精製反応生成物(97GC％)397g(収率78％)を得た。 After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 145 to 155 ° C., and a tower top temperature of 138 to 141 ° C., and the distillation fraction was washed with water to give a purified reaction product (97 GC% ) 397 g (yield 78%) was obtained.
得られた精製反応生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる化合物であることが確認された。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2
1H-NMR(CD3OD、TMS)：δ3.34(CH 2CF2)
2.42(CH 2CH2)
2.07(CH2CH 2)
4.13(CH 2CH3)
1.36(CH2CH 3)
19F-NMR(CD3OD、C6F6):ppm -85.3(CF 3)
-114.0(CF3CF 2CH2CF2)
-110.1(CH2CF 2CF2CF2CF2CF2)
-120.1(CH2CF2CF 2CF2CF2CF2)
-122.0(CH2CF2CF2CF 2CF2CF2)
-122.4(CH2CF2CF2CF2CF 2CF2)
-113.9(CH2CF2CF2CF2CF2CF 2)
The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
1 H-NMR (CD 3 OD, TMS): δ 3.34 (C H 2 CF 2 )
2.42 (C H 2 CH 2 )
2.07 (CH 2 C H 2 )
4.13 (C H 2 CH 3 )
1.36 (CH 2 C H 3 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -85.3 (C F 3 )
-114.0 (CF 3 C F 2 CH 2 CF 2 )
-110.1 (CH 2 C F 2 CF 2 CF 2 CF 2 CF 2 )
-120.1 (CH 2 CF 2 C F 2 CF 2 CF 2 CF 2 )
-122.0 (CH 2 CF 2 CF 2 C F 2 CF 2 CF 2 )
-122.4 (CH 2 CF 2 CF 2 CF 2 C F 2 CF 2 )
-113.9 (CH 2 CF 2 CF 2 CF 2 CF 2 C F 2 )
参考例５
温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)I (98GC％)
500g(1.12モル)およびトリエチルホスファイトP(OC2H5)3 259g(2.24モル)を仕込み、155℃で攪拌した。このとき、副生生物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に130g(1.12モル)宛4回分添し、合計18時間攪拌した。
Reference Example 5
In a 1 L four-necked flask equipped with a thermometer and a low-boiler removal receiver,
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I (98GC%)
500 g (1.12 mol) and triethyl phosphite P (OC 2 H 5 ) 3 259 g (2.24 mol) were charged and stirred at 155 ° C. At this time, in order to remove ethyl iodide as a by-product from the reaction system, nitrogen gas was bubbled into the reaction solution using a thin tube. A small amount of the reaction solution was collected and subjected to gas chromatography analysis. After confirming the remaining amount of triethyl phosphite, triethyl phosphite was further added four times to 130 g (1.12 mol) at a time and stirred for a total of 18 hours. .
反応終了後、反応混合物を内圧0.2kPa、内温130〜140℃、塔頂温度128〜131℃の条件下で減圧単蒸留を行い、蒸留留分を水洗して、精製反応生成物(98GC％)405g(収率79％)を得た。 After completion of the reaction, the reaction mixture was subjected to vacuum simple distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 130 to 140 ° C., and a tower top temperature of 128 to 131 ° C., and the distillation fraction was washed with water to obtain a purified reaction product (98 GC% ) 405 g (yield 79%) was obtained.
得られた精製反応生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる化合物であることが確認された。
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2
1H-NMR(CD3OD、TMS)：δ3.34(CH 2CF2)
2.42(CH 2CH2)
2.07(CH2CH 2)
4.13(CH 2CH3)
1.36(CH2CH 3)
19F-NMR(CD3OD、C6F6):ppm -85.3(CF 3)
-114.0(CF3CF 2CH2CF2)
-110.4(CH2CF 2CF2CF2)
-122.4(CH2CF2CF 2CF2)
-113.9(CH2CF2CF2CF 2)
The obtained purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
1 H-NMR (CD 3 OD, TMS): δ 3.34 (C H 2 CF 2 )
2.42 (C H 2 CH 2 )
2.07 (CH 2 C H 2 )
4.13 (C H 2 CH 3 )
1.36 (CH 2 C H 3 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -85.3 (C F 3 )
-114.0 (CF 3 C F 2 CH 2 CF 2 )
-110.4 (CH 2 C F 2 CF 2 CF 2 )
-122.4 (CH 2 CF 2 C F 2 CF 2 )
-113.9 (CH 2 CF 2 CF 2 C F 2 )
実施例１
温度計およびコンデンサを備えた容量1Lの四口フラスコ中に、参考例１で得られたホスホン酸ジエステル
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2 (96GC％)
300g(0.44モル)および約35％濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分276gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物242g(0.41モル、収率92％)を得た。
Example 1
Phosphonic acid diester obtained in Reference Example 1 in a 1 L four-necked flask equipped with a thermometer and a condenser
CF 3 (CF 2) 3 ( CH 2 CF 2) (CF 2 CF 2) 2 (CH 2 CH 2) P (O) (OCH 2 CH 3) 2 (96GC%)
300 g (0.44 mol) and about 35% concentrated hydrochloric acid 300 g were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 276 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 242 g (0.41 mol, yield 92%) of the desired product.
得られた生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる目的化合物であることが確認された。
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)2
1H-NMR(CD3OD、TMS)：δ3.44(CH 2CF2)
2.44(CH 2CH2)
1.93(CH2CH 2)
19F-NMR(CD3OD、C6F6):ppm -80.2(CF 3)
-124.6(CF3CF 2CF2CF2)
-122.3(CF3CF2CF 2CF2)
-110.0(CF 2CH2CF2)
-110.0(CF2CH2CF 2)
-120.0(CH2CF2CF 2CF2)
-121.6(CH2CF2CF2CF 2)
-122.3(CF 2CF2CH2CH2)
-113.9(CF2CF 2CH2CH2)
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be the target compound represented by the following formula.
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OH) 2
1 H-NMR (CD 3 OD, TMS): δ3.44 (C H 2 CF 2 )
2.44 (C H 2 CH 2 )
1.93 (CH 2 C H 2 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -80.2 (C F 3 )
-124.6 (CF 3 C F 2 CF 2 CF 2 )
-122.3 (CF 3 CF 2 C F 2 CF 2 )
-110.0 (C F 2 CH 2 CF 2 )
-110.0 (CF 2 CH 2 C F 2 )
-120.0 (CH 2 CF 2 C F 2 CF 2 )
-121.6 (CH 2 CF 2 CF 2 C F 2 )
-122.3 (C F 2 CF 2 CH 2 CH 2 )
-113.9 (CF 2 C F 2 CH 2 CH 2 )
実施例２
温度計およびコンデンサを備えた容量1Lの四口フラスコ中に、参考例２で得られたホスホン酸ジエステル
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2 (96GC％)
300g(0.53モル)および約35％濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分287gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物240g(0.49モル、収率93％)を得た。
Example 2
Phosphonic acid diester obtained in Reference Example 2 in a 1 L four-necked flask equipped with a thermometer and condenser
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2 (96GC%)
300 g (0.53 mol) and about 35% concentrated hydrochloric acid 300 g were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover 287 g of a solid content. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 240 g (0.49 mol, yield 93%) of the desired product.
得られた生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる目的化合物であることが確認された。
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2
1H-NMR(CD3OD、TMS)：δ3.44(CH 2CF2)
2.45(CH 2CH2)
1.93(CH2CH 2)
19F-NMR(CD3OD、C6F6):ppm -80.2(CF 3)
-124.0(CF3CF 2CF2CF2)
-122.3(CF3CF2CF 2CF2)
-110.3(CF 2CH2CF2)
-119.8(CF2CH2CF 2)
-124.6(CF 2CF2CH2CH2)
-113.2(CF2CF 2CH2CH2)
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be the target compound represented by the following formula.
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OH) 2
1 H-NMR (CD 3 OD, TMS): δ3.44 (C H 2 CF 2 )
2.45 (C H 2 CH 2 )
1.93 (CH 2 C H 2 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -80.2 (C F 3 )
-124.0 (CF 3 C F 2 CF 2 CF 2 )
-122.3 (CF 3 CF 2 C F 2 CF 2 )
-110.3 (C F 2 CH 2 CF 2 )
-119.8 (CF 2 CH 2 C F 2 )
-124.6 (C F 2 CF 2 CH 2 CH 2 )
-113.2 (CF 2 C F 2 CH 2 CH 2 )
実施例３
温度計およびコンデンサを備えた容量1Lの四口フラスコ中に、参考例３で得られたホスホン酸ジエステル
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OCH2CH3)2 (96GC％)
300g(0.44モル)および約35％濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分276gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物237g(0.40モル、収率90％)を得た。
Example 3
Phosphonic acid diester obtained in Reference Example 3 in a 1 L four-necked flask equipped with a thermometer and a condenser
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2 (96GC%)
300 g (0.44 mol) and about 35% concentrated hydrochloric acid 300 g were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 276 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 237 g (0.40 mol, yield 90%) of the desired product.
得られた生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる目的化合物であることが確認された。
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OH)2
1H-NMR(CD3OD、TMS)：δ3.41(CH 2CF2)
2.44(CH 2CH2)
1.93(CH2CH 2)
19F-NMR(CD3OD、C6F6):ppm -85.3(CF 3CF2)
-114.0(CF3CF 2)
-110.2(CH2CF 2CF2CF2CF2CF2CF2CF2)
-120.0(CH2CF2CF 2CF2CF2CF2CF2CF2)
-119.5(CH2CF2CF2CF 2CF2CF2CF2CF2)
-120.3(CH2CF2CF2CF2CF 2CF2CF2CF2)
-121.4(CH2CF2CF2CF2CF2CF 2CF2CF2)
-122.2(CH2CF2CF2CF2CF2CF2CF 2CF2)
-114.7(CH2CF2CF2CF2CF2CF2CF2CF 2)
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be the target compound represented by the following formula.
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) P (O) (OH) 2
1 H-NMR (CD 3 OD, TMS): δ3.41 (C H 2 CF 2 )
2.44 (C H 2 CH 2 )
1.93 (CH 2 C H 2 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -85.3 (C F 3 CF 2 )
-114.0 (CF 3 C F 2 )
-110.2 (CH 2 C F 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )
-120.0 (CH 2 CF 2 C F 2 CF 2 CF 2 CF 2 CF 2 CF 2 )
-119.5 (CH 2 CF 2 CF 2 C F 2 CF 2 CF 2 CF 2 CF 2 )
-120.3 (CH 2 CF 2 CF 2 CF 2 C F 2 CF 2 CF 2 CF 2 )
-121.4 (CH 2 CF 2 CF 2 CF 2 CF 2 C F 2 CF 2 CF 2 )
-122.2 (CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 C F 2 CF 2 )
-114.7 (CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 C F 2 )
実施例４
温度計およびコンデンサを備えた容量1Lの四口フラスコ中に、参考例４で得られたホスホン酸ジエステル
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2 (95GC％)
300g(0.52モル)および約35％濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分271gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物235g(0.48モル、収率92％)を得た。
Example 4
Phosphonic acid diester obtained in Reference Example 4 in a 1 L four-necked flask equipped with a thermometer and a condenser
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2 (95GC%)
300 g (0.52 mol) and 300 g of about 35% concentrated hydrochloric acid were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 271 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 235 g (0.48 mol, yield 92%) of the desired product.
得られた生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる目的化合物であることが確認された。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)2
1H-NMR(CD3OD、TMS)：δ3.41(CH 2CF2)
2.44(CH 2CH2)
1.93(CH2CH 2)
19F-NMR(CD3OD、C6F6):ppm -85.3(CF 3CF2)
-114.0(CF3CF 2)
-110.1(CH2CF 2CF2CF2CF2CF2)
-120.1(CH2CF2CF 2CF2CF2CF2)
-122.0(CH2CF2CF2CF 2CF2CF2)
-122.6(CH2CF2CF2CF2CF 2CF2)
-114.7(CH2CF2CF2CF2CF2CF 2)
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be the target compound represented by the following formula.
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OH) 2
1 H-NMR (CD 3 OD, TMS): δ3.41 (C H 2 CF 2 )
2.44 (C H 2 CH 2 )
1.93 (CH 2 C H 2 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -85.3 (C F 3 CF 2 )
-114.0 (CF 3 C F 2 )
-110.1 (CH 2 C F 2 CF 2 CF 2 CF 2 CF 2 )
-120.1 (CH 2 CF 2 C F 2 CF 2 CF 2 CF 2 )
-122.0 (CH 2 CF 2 CF 2 C F 2 CF 2 CF 2 )
-122.6 (CH 2 CF 2 CF 2 CF 2 C F 2 CF 2 )
-114.7 (CH 2 CF 2 CF 2 CF 2 CF 2 C F 2 )
実施例５
温度計およびコンデンサを備えた容量1Lの四口フラスコ中に、参考例５で得られたホスホン酸ジエステル
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2 (94GC％)
300g(0.63モル)および約35％濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分262gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物229g(0.59モル、収率93％)を得た。
Example 5
Phosphonic acid diester obtained in Reference Example 5 in a 1 L four-necked flask equipped with a thermometer and a condenser
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2 (94GC%)
300 g (0.63 mol) and 300 g of about 35% concentrated hydrochloric acid were charged and stirred at 100 ° C. for 12 hours. After cooling, the mixture was filtered under reduced pressure to recover a solid content of 262 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 229 g (0.59 mol, yield 93%) of the desired product.
得られた生成物は、1H-NMRおよび19F-NMRの結果から、次式で表わされる目的化合物であることが確認された。
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2
1H-NMR(CD3OD、TMS)：δ3.41(CH 2CF2)
2.44(CH 2CH2)
1.93(CH2CH 2)
19F-NMR(CD3OD、C6F6):ppm -85.3(CF 3CF2)
-114.0(CF3CF 2)
-110.4(CH2CF 2CF2CF2)
-122.6(CH2CF2CF 2CF2)
-114.0(CH2CF2CF2CF 2)
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be the target compound represented by the following formula.
CF 3 (CF 2) (CH 2 CF 2) (CF 2 CF 2) (CH 2 CH 2) P (O) (OH) 2
1 H-NMR (CD 3 OD, TMS): δ3.41 (C H 2 CF 2 )
2.44 (C H 2 CH 2 )
1.93 (CH 2 C H 2 )
19 F-NMR (CD 3 OD, C 6 F 6 ): ppm -85.3 (C F 3 CF 2 )
-114.0 (CF 3 C F 2 )
-110.4 (CH 2 C F 2 CF 2 CF 2 )
-122.6 (CH 2 CF 2 C F 2 CF 2 )
-114.0 (CH 2 CF 2 CF 2 C F 2 )
参考例６
前記実施例１で得られたポリフルオロアルキルホスホン酸20重量％にイソプロパノール50重量％を加えた後、攪拌しながらイオン交換水26重量％を加え、トリエチルアミン4重量％で中和して、A液(合計100重量％)とした。このA液を水で希釈し、固形分濃度を0.1重量％として、離型剤を調製した。
Reference Example 6
After adding 50% by weight of isopropanol to 20% by weight of the polyfluoroalkylphosphonic acid obtained in Example 1, 26% by weight of ion-exchanged water was added while stirring, and neutralized with 4% by weight of triethylamine, (Total 100% by weight). The release liquid was prepared by diluting this liquid A with water to a solid content concentration of 0.1% by weight.
この離型剤を用いてのウレタンゴム成形時の離型試験を、次のように実施した。直径45mm、深さ50mmのアルミニウム製カップを成形型とし、この型を80℃に加熱した後離型剤を塗布して、80℃で乾燥させた。この離型剤塗布型内に、80℃に加熱したウレタンゴム(日本ポリウレタン製品コロネート4090)100重量部と120℃に加熱した硬化剤(イハラケミカル製品イハラキュアミンMT)12.8重量部との混合物10gを注入し、120℃で1時間加熱硬化させた。 A mold release test at the time of molding urethane rubber using this mold release agent was performed as follows. An aluminum cup having a diameter of 45 mm and a depth of 50 mm was used as a mold, the mold was heated to 80 ° C., a release agent was applied, and the mold was dried at 80 ° C. In this release agent coating mold, 10 g of a mixture of 100 parts by weight of urethane rubber (Japanese polyurethane product Coronate 4090) heated to 80 ° C and 12.8 parts by weight of a curing agent (Ihara Chemical product Iharacamine MT) heated to 120 ° C Was injected and cured at 120 ° C. for 1 hour.
硬化前に、注入部中央に硬化成形品取出し用のフックが設置させており、硬化後にそのフックを引っ張って成形品を型から取出す際の荷重を上方に位置するバネ秤で求めると、0.4kgfという値(離型性能)が得られた。また離型剤を最初1回塗布した後、5kgf以下の離型荷重で何回迄離型できるかの回数を測定すると、10回という値(離型寿命)が得られた。 Before curing, a hook for taking out the cured molded product is installed in the center of the injection part.After curing, the load when the molded product is taken out from the mold by pulling the hook is 0.4 kgf The value (release performance) was obtained. When the number of times the mold could be released with a release load of 5 kgf or less was measured after first applying the release agent, a value of 10 times (release life) was obtained.
Claims (2)
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2 〔I〕
(ここで、nは1〜6の整数、aは1〜4の整数、bは1〜3の整数、cは1〜3の整数である)で表わされるポリフルオロアルキルホスホン酸。 General formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OH) 2 (I)
(Where n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3).
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OR)2 〔II〕
(ここで、Rは炭素数1〜4のアルキル基であり、nは1〜6の整数、aは1〜4の整数、bは1〜3の整数、cは1〜3の整数である)で表わされるポリフルオロアルキルホスホン酸ジエステルを加水分解反応させることを特徴とする請求項１記載のポリフルオロアルキルホスホン酸の製造法。 General formula
C n F 2n + 1 (CH 2 CF 2) a (CF 2 CF 2) b (CH 2 CH 2) c P (O) (OR) 2 (II)
(Where R is an alkyl group having 1 to 4 carbon atoms, n is an integer of 1 to 6, a is an integer of 1 to 4, b is an integer of 1 to 3, and c is an integer of 1 to 3) A process for producing a polyfluoroalkylphosphonic acid according to claim 1, wherein the polyfluoroalkylphosphonic acid diester represented by formula (1) is hydrolyzed.
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| JP2009060481A JP4506893B1 (en) | 2009-03-13 | 2009-03-13 | Polyfluoroalkylphosphonic acid and process for producing the same |
| US13/255,332 US8197586B2 (en) | 2009-03-13 | 2010-03-09 | Polyfluoroalkylphosphonic acid, method for producing the same and mold-releasing agent comprising the same as active ingredient |
| CN201080011731.6A CN102348711B (en) | 2009-03-13 | 2010-03-09 | Polyfluoroalkylphosphonic acid, method for producing same and mold-releasing agent comprising same as active ingredient |
| CA2753117A CA2753117C (en) | 2009-03-13 | 2010-03-09 | Polyfluoroalkylphosphonic acid, method for producing the same and mold-releasing agent comprising the same as active ingredient |
| EP10750818.6A EP2407472B1 (en) | 2009-03-13 | 2010-03-09 | Polyfluoroalkylphosphonic acid, method for producing same and mold-releasing agent comprising same as active ingredient |
| PCT/JP2010/053871 WO2010104065A1 (en) | 2009-03-13 | 2010-03-09 | Polyfluoroalkylphosphonic acid, method for producing same and mold-releasing agent comprising same as active ingredient |
| KR1020117018811A KR101297593B1 (en) | 2009-03-13 | 2010-03-09 | Polyfluoroalkylphosphonic acid, method for producing same and mold-releasing agent comprising same as active ingredient |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017119371A1 (en) * | 2016-01-08 | 2017-07-13 | 東ソー・エフテック株式会社 | Novel fluorinated compound having unsaturated bond, and surface modifier using same |
| JP7649683B2 (en) | 2020-06-17 | 2025-03-21 | 東ソー・ファインケム株式会社 | Fluorine-containing ammonium salt, aqueous composition using same, and surface modifier |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005528446A (en) * | 2002-05-31 | 2005-09-22 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated phosphonic acid |
| WO2007105633A1 (en) * | 2006-03-10 | 2007-09-20 | Unimatec Co., Ltd. | Polyfluoroalkyl alcohol or (meth)acrylic acid derivative thereof, and their production methods |
-
2009
- 2009-03-13 JP JP2009060481A patent/JP4506893B1/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005528446A (en) * | 2002-05-31 | 2005-09-22 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated phosphonic acid |
| WO2007105633A1 (en) * | 2006-03-10 | 2007-09-20 | Unimatec Co., Ltd. | Polyfluoroalkyl alcohol or (meth)acrylic acid derivative thereof, and their production methods |
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