JP4711011B2 - Polyfluoroalkylphosphonic acid oxyalkylene ester and process for producing the same - Google Patents
Polyfluoroalkylphosphonic acid oxyalkylene ester and process for producing the same Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims description 37
- -1 oxyalkylene ester Chemical class 0.000 title claims description 23
- 238000000034 method Methods 0.000 title description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 9
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000047 product Substances 0.000 description 67
- 238000006243 chemical reaction Methods 0.000 description 50
- 150000001875 compounds Chemical class 0.000 description 37
- 239000000203 mixture Substances 0.000 description 33
- 239000011541 reaction mixture Substances 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 23
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000004262 preparative liquid chromatography Methods 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 10
- 150000005690 diesters Chemical class 0.000 description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 9
- 150000002978 peroxides Chemical class 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 6
- 239000006082 mold release agent Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000001577 simple distillation Methods 0.000 description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 231100000693 bioaccumulation Toxicity 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000001993 wax Substances 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 239000009261 D 400 Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 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
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical group CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012934 organic peroxide initiator Substances 0.000 description 1
- 239000003960 organic solvent Substances 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
- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 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
- 230000003578 releasing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
Description
本発明は、ポリフルオロアルキルホスホン酸オキシアルキレンエステル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有効に用いられるポリフルオロアルキルホスホン酸オキシアルキレンエステルおよびその製造法に関する。 The present invention relates to a polyfluoroalkylphosphonic acid oxyalkylene ester and a method for producing the same. More specifically, the present invention relates to a polyfluoroalkylphosphonic acid oxyalkylene ester which is effectively used as an active ingredient of a release agent and a production method thereof.
現在、プラスチック材料やゴム材料などの高分子材料を、金型を用いて成形する際に、シリコーン油、ワックス、タルク、マイカ、テトラフルオロエチレン樹脂などの離型剤が用いられている。しかしながら、シリコーン油、ワックスなどは良好な離型性を示すものの、離型剤が成形品に移行するため、均一塗装性、二次加工性などを損なわせ、また持続性の点で欠けるものがある。また、テトラフルオロエチレン樹脂では、離型効果の持続性や二次加工性の点では満足されるものの、離型処理時に金型の型面に膜状の焼付処理をしなければならず、再処理時にも同様の処理が必要となるため、操作工程が多くなるという問題点がみられる。 Currently, release agents such as silicone oil, wax, talc, mica, and tetrafluoroethylene resin are used when polymer materials such as plastic materials and rubber materials are molded using a mold. However, although silicone oil, wax, etc. show good releasability, the mold release agent moves to the molded product, so that uniform paintability, secondary processability, etc. are impaired, and there are things that are lacking in sustainability. is there. Also, the tetrafluoroethylene resin, although in terms of sustainability and secondary processability of the releasing effect is satisfied, it is necessary to the film-like baking process in the mold surface of the mold during the mold release process, re Since the same processing is required at the time of processing, there is a problem that the number of operation steps increases .
かかる欠点を解消させるために、炭素数4〜20のポリフルオロアルキル基含有リン酸エステルを有効成分の一つとする離型剤が提案されている(特許文献１〜３参照)。これらの離型剤は、良好な離型性を示し、また従来のものと比べて離型寿命が長いとされてはいるものの、昨今の成形品形状の複雑化に伴い、離型剤としてなお一層の性能の向上が求められている。 In order to eliminate such drawbacks, a mold release agent having a polyfluoroalkyl group-containing phosphate ester having 4 to 20 carbon atoms as one of active ingredients has been proposed (see Patent Documents 1 to 3). Although these mold release agents exhibit good mold release properties and have a longer mold release life than conventional ones, they are still used as mold release agents as the shape of molded products has become more complex. There is a need for further improvement in performance.
一方、ポリフルオロアルキルホスホン酸エステルも、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のパーフルオロオクチル基を有するホスホン酸エステル化合物である
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４〜７参照)。
On the other hand, polyfluoroalkylphosphonic acid esters are also 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 a compound having 8 to 12 carbon atoms in the perfluoroalkyl group, particularly a phosphonate compound having a C 8 perfluorooctyl group.
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 4 to 7).
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リン酸エステル化合物またはホスホン酸エステル化合物は、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、処理工程での暴露や廃棄物、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, a phosphate ester compound or a phosphonate ester compound having a perfluoroalkyl group having 8 to 12 carbon atoms can be biodegraded in the environment and changed into a compound having relatively high bioaccumulation and environmental concentration. have been reported, exposure and waste in the process, release, diffusion and the like are environmental concerns from the treated substrate or the like. 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リン酸エステル化合物またはホスホン酸エステル化合物は、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、このようなリン酸エステルまたはホスホン酸エステル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, a phosphoric acid ester compound or a phosphonic acid ester compound having a perfluoroalkyl group having 8 or more carbon atoms inevitably generates or mixes perfluorooctanoic acids having high bioaccumulation potential in the production process. Therefore, manufacturers of such phosphoric acid ester or phosphonic acid ester 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、離型剤の有効成分として用いたとき、炭素数8以上のパーフルオロアルキル基を有する化合物と同等の離型性能を発揮するポリフルオロアルキルホスホン酸エステル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 properties. When used as an active ingredient of a release agent, a perfluoroalkyl group having 8 or more carbon atoms is used. It is an object of the present invention to provide a polyfluoroalkylphosphonic acid ester that exhibits mold release performance equivalent to that of a compound having the same and a method for producing the same.
本発明によって、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)〔O(RO)mR′〕d(OH)2-d
(ここで、ROは炭素数2〜6の直鎖状または分岐状オキシアルキレン基であり、R′は水素原子または炭素数1〜20のアルキル基またはアラルキル基であり、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、mは1〜100の整数、dは1または2である)で表わされるポリフルオロアルキルホスホン酸オキシアルキレンエステルが提供される。
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) [O (RO) m R ′] d (OH) 2-d
(Wherein RO is a linear or branched oxyalkylene group having 2 to 6 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and n is 1 to 6 carbon atoms. An integer of 1 to 4, b is an integer of 1 to 3, c is an integer of 1 to 3, m is an integer of 1 to 100, and d is 1 or 2. Oxyalkylene esters are provided.
かかるポリフルオロアルキルホスホン酸オキシアルキレンエステルは、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2
で表わされるポリフルオロアルキルホスホン酸と一般式
HO(RO)mR′
で表わされるポリアルキレングリコールまたはそのモノエーテルとを縮合反応させることにより製造される。
Such polyfluoroalkylphosphonic acid oxyalkylene esters 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) (OH) 2
A polyfluoroalkylphosphonic acid represented by the general formula
HO (RO) m R ′
Is produced by a condensation reaction with a polyalkylene glycol represented by the formula:
本発明に係るポリフルオロアルキルホスホン酸オキシアルキレンエステルは、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オリゴマー化合物であって、これを離型剤の有効成分として用いたとき、1.0重量％程度の低濃度でも、すぐれた離型性、持続性を発揮するため、離型剤による型汚れの低減、成形品の寸法精度の向上などが達成される。 The polyfluoroalkylphosphonic acid oxyalkylene ester according to the present invention is an oligomer compound having a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation, and is used as an active ingredient of a release agent. Even at a low concentration of about 1.0% by weight, excellent mold releasability and durability are exhibited, so that reduction of mold contamination by the release agent and improvement of the dimensional accuracy of the molded product are achieved.
さらに、成形品の電気接点不良という問題もなく、二次加硫性にもすぐれている。 Furthermore, there is no problem of defective electrical contact of the molded product, and the secondary vulcanizability is excellent.
ポリフルオロアルキルホスホン酸
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2 〔I〕
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。
Polyfluoroalkylphosphonic acid
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)
Is 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.
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８に記載されている。
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 8.
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、反応の進捗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 in a proportion of about 1 to 5 mol% with respect to the compound [IV] from the viewpoint of the progress 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 lower-priced material, it is possible to reduce the capital investment cost at a lower cost 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、一方の反応原料とな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, polyfluoroalkylphosphonic acid [I] as one reaction raw material is obtained in a good yield of 90% by a method such as washing with water and filtration, washing with acetone and filtration. be able to.
他方の反応原料となる、一般式
HO(RO)mR′ 〔X〕
で表わされるポリアルキレングリコールまたはそのモノエーテルとしては、例えばポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、ポリヘキシレングリコールまたはこれらのモノアルキルエーテルまたはモノアラルキルエーテル、好ましくはモノメチルエーテル、モノエチルエーテル等であって、mが1〜100のもの、好ましくは数平均分子量Mnが約200〜4000のものが用いられる。
The general formula for the other reaction raw material
HO (RO) m R ′ (X)
Examples of the polyalkylene glycol represented by the formula (1) include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyhexylene glycol, and monoalkyl ethers or monoaralkyl ethers thereof, preferably monomethyl ether, monoethyl ether, and the like. And m having a number average molecular weight Mn of about 200 to 4000 is preferably used.
ポリフルオロアルキルホスホン酸〔I〕とポリアルキレングリコールまたはそのモノエーテル〔X〕との間の縮合反応は、濃硫酸、濃塩酸等の脱水触媒を用い、約80〜180℃の温度に加熱することによって行われる。反応に際しては、窒素バブリング等を継続して行い、生成した水を反応系外に追い出すことによって、脱水縮合反応を進行させる。 The condensation reaction between polyfluoroalkylphosphonic acid [I] and polyalkylene glycol or its monoether [X] is heated to a temperature of about 80 to 180 ° C. using a dehydration catalyst such as concentrated sulfuric acid or concentrated hydrochloric acid. Is done by. In the reaction, nitrogen bubbling or the like is continuously performed, and the generated water is driven out of the reaction system to advance the dehydration condensation reaction.
反応混合物は、約50重量％程度の未反応ポリアルキレングリコール(モノエーテル)および約50重量％程度の反応生成物よりなり、反応生成物は、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)〔O(RO)mR′〕(OH)
で表わされるポリフルオロアルキルホスホン酸モノオキシアルキレンエステル〔A〕と一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)〔O(RO)mR′〕2
で表わされるポリフルオロアルキルホスホン酸ビス(オキシアルキレン)エステル〔B〕との混合物よりなる。
The reaction mixture is composed of about 50% by weight of unreacted polyalkylene glycol (monoether) and about 50% by weight of the reaction product.
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) [O (RO) m R ′] (OH)
A polyfluoroalkylphosphonic acid monooxyalkylene ester [A] represented by 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) [O (RO) m R ′] 2
And a mixture with a polyfluoroalkylphosphonic acid bis (oxyalkylene) ester [B].
ポリアルキレングリコール(モノエーテル)〔X〕は、ポリフルオロアルキルホスホン酸〔I〕に対して等モル量以上用いられ、そのモル比が2程度、一般には約1.5〜2.5程度のモル比で用いられた場合には、主としてモノオキシアルキレンエステル〔A〕が生成し、そのモル比が4程度、一般には約3.0〜4.5程度のモル比で用いられた場合には、主としてビス(オキシアルキレン)エステル〔B〕が生成する。 Polyalkylene glycol (monoether) [X] is used in an equimolar amount or more with respect to polyfluoroalkylphosphonic acid [I], and its molar ratio is about 2, generally about 1.5 to 2.5. If the the mono-polyoxyalkylene ester [a] is produced mainly in a molar ratio of about 4, if the generally used in a molar ratio of about 3.0 to 4.5 are mainly bis (oxyalkylene) esters [ B] is generated.
モノエーテル化されていないポリアルキレングリコールが用いられた場合にも、使用されたモル比に応じて、主としてモノオキシアルキレンエステル〔A〕またはビス(オキシアルキレン)エステル〔B〕が生成するが、同時に両末端グリコール基にそれぞれポリフルオロアルキルホスホン酸が縮合して付加された生成物〔C〕も少量ではあるが生成される。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)-O(RO)m-
P(O)(OH)-(CH2CH2)c(CF2CF2)b(CF2CH2)aCnF2n+1
Even when a polyalkylene glycol that is not monoetherified is used, depending on the molar ratio used, mainly a monooxyalkylene ester [A] or a bis (oxyalkylene) ester [B] is produced. A product [C] in which polyfluoroalkylphosphonic acid is condensed and added to both terminal glycol groups is also produced in a small amount.
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OH) -O (RO) m-
P (O) (OH)-(CH 2 CH 2 ) c (CF 2 CF 2 ) b (CF 2 CH 2 ) a C n F 2n + 1
反応混合物からの未反応ポリアルキレングルコール(モノエーテル)、ポリフルオロアルキルホスホン酸のモノオキシアルキレンエステルおよびビス(オキシアルキレン)エステルの分離は、それぞれ分取液体クロマトグラフィーを用いて行われる。 Unreacted polyalkylene glycol from the reaction mixture (monoether), separation of mono- oxyalkylene ester and bis (oxyalkylene) esters of polyfluoroalkyl phosphonic acid is carried out using preparative liquid chromatography respectively minute.
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
(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、
C4F9(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
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
C 4 F 9 (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。
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)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.
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
(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、得られたホスホン酸ジエステル
C4F9(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。
(2) Obtained phosphonic acid diester in a 1 L four-necked flask equipped with a thermometer and a condenser.
C 4 F 9 (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、次式で表わされる化合物(ポリフルオロアルキルホスホン酸A；MW592、F含量61.0重量％)であることが確認された。
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)2
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be a compound represented by the following formula (polyfluoroalkylphosphonic acid A; MW592, F content 61.0 wt%).
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OH) 2
参考例２
(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、
C4F9(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
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
C 4 F 9 (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。
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)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.
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
(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、得られたホスホン酸ジエステル
C4F9(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。
(2) Obtained phosphonic acid diester in a 1 L four-necked flask equipped with a thermometer and a condenser.
C 4 F 9 (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、次式で表わされる化合物(ポリフルオロアルキルホスホン酸B；MW492、F含量57.9重量％)であることが確認された。
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be a compound represented by the following formula (polyfluoroalkylphosphonic acid B; MW492, F content 57.9 wt%).
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OH) 2
参考例３
(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、
C2F5(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
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
C 2 F 5 (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。
C2F5(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OCH2CH3)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.
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
(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、得られたホスホン酸ジエステル
C2F5(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。
(2) Obtained phosphonic acid diester in a 1 L four-necked flask equipped with a thermometer and a condenser.
C 2 F 5 (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、次式で表わされる化合物(ポリフルオロアルキルホスホン酸C；MW592、F含量61.0重量％)であることが確認された。
C2F5(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OH)2
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be a compound represented by the following formula (polyfluoroalkylphosphonic acid C; MW592, F content 61.0 wt%).
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) P (O) (OH) 2
参考例４
(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、
C2F5(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
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
C 2 F 5 (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。
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)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.
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
(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、得られたホスホン酸ジエステル
C2F5(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。
(2) Obtained phosphonic acid diester in a 1 L four-necked flask equipped with a thermometer and a condenser.
C 2 F 5 (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(ポリフルオロアルキルホスホン酸D；MW492、F含量57.9重量％)であることが確認された。
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)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 (polyfluoroalkylphosphonic acid D; MW492, F content 57.9 wt%). .
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (OH) 2
参考例５
(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、
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)2I (97GC％)
500g(0.88モル)およびトリエチルホスファイトP(OC2H5)3 204g(1.76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 5
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 I (97GC%)
500 g (0.88 mol) and triethyl phosphite P (OC 2 H 5 ) 3 204 g (1.76 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140〜142℃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(97GC％)410g(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 140 to 142 ° C., and the distillation fraction was washed with water to give a purified reaction product (97 GC% 410 g (79% yield).
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。
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OCH2CH3)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.
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 P (O) (OCH 2 CH 3 ) 2
(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、得られたホスホン酸ジエステル
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OCH2CH3)2 (97GC％)
300g(0.51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269g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(0.46モル、収率90％)を得た。
(2) Obtained phosphonic acid diester in a 1 L four-necked flask equipped with a thermometer and a condenser.
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 P (O) (OCH 2 CH 3 ) 2 (97GC%)
300 g (0.51 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 269 g. This solid content was washed with water and filtered again, and further washed with acetone and filtered to obtain 240 g (0.46 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(ポリフルオロアルキルホスホン酸E；MW553、F含量51.5重量％)であることが確認された。
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OH)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 (polyfluoroalkylphosphonic acid E; MW553, F content 51.5 wt%). .
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 P (O) (OH) 2
参考例６
(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、
C2F5(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 6
(1) In a 1 L four-necked flask equipped with a thermometer and a low boiling point removal receiver,
C 2 F 5 (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。
C2F5(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)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.
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OCH 2 CH 3 ) 2
(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、得られたホスホン酸ジエステル
C2F5(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。
(2) Obtained phosphonic acid diester in a 1 L four-necked flask equipped with a thermometer and a condenser.
C 2 F 5 (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、次式で表わされる化合物(ポリフルオロアルキルホスホン酸F；MW392、F含量53.3重量％)であることが確認された。
C2F5(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2
From the results of 1 H-NMR and 19 F-NMR, the obtained product was confirmed to be a compound represented by the following formula (polyfluoroalkylphosphonic acid F; MW392, F content 53.3 wt%).
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (OH) 2
実施例１
攪拌機、窒素バブリング装置および温度計を備えた容量500mlの反応容器内に、前記参考例１(2)で得られたポリフルオロアルキルホスホン酸A 112g(0.19モル)およびポリエチレングリコールモノメチルエーテル〔PEG-a〕(日油製品ユニオックスM-550；MW=496、m=約12)
HO(CH2CH2O)mCH3
188g(0.38モル)を仕込み、70℃に加温した後、窒素バブリングを行った。その後、反応容器内温を155℃まで昇温させ、濃硫酸1.2gを添加した。反応継続中窒素バブリングを続けることにより、反応で生成した水を反応系外に追い出しながら、48時間反応を継続した。
Example 1
In a 500 ml reaction vessel equipped with a stirrer, a nitrogen bubbling device and a thermometer, 112 g (0.19 mol) of polyfluoroalkylphosphonic acid A obtained in Reference Example 1 (2) and polyethylene glycol monomethyl ether [PEG-a ] (Nippon Oil Products UNIOX M-550; MW = 496, m = about 12)
HO (CH 2 CH 2 O) m CH 3
After charging 188 g (0.38 mol) and heating to 70 ° C., nitrogen bubbling was performed. Thereafter, the temperature inside the reaction vessel was raised to 155 ° C., and 1.2 g of concentrated sulfuric acid was added. By continuing nitrogen bubbling during the reaction, the reaction was continued for 48 hours while water generated by the reaction was driven out of the reaction system.
反応終了後冷却し、淡黄色ワックス状の反応混合物(混合物中のF含量22.4重量％)を275g(回収率92％)得た。得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-a／生成物Ia／生成物Ib=重量比50/48/2であった。
生成物Ia(m=約12)：
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物Ib(m=約12)：
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕2
19F-NMR；δ= 82.0(3F：CF 3-)
-113.1(4F：-CF 2CH2CF 2-)
-114.5(2F：-CF2CF 2CH2CH2-)
-121.9〜-127.0(10F：-CF 2-)
1H-NMR；δ= 1.74(2H：-CF2CH2CH 2-)
2.25(2H：-CF2CH 2CH2-)
2.90(2H：-CF2CH 2CF2-)
3.25(3H：-OCH 3)
3.20〜3.70(48H：-OCH 2CH2O-、-OCH2CH 2O-)
4.10(2H：-P(O)OCH 2CH2-)
After completion of the reaction, the reaction mixture was cooled to obtain 275 g (recovery rate: 92%) of a pale yellow wax-like reaction mixture (F content in the mixture: 22.4% by weight). The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-a / product Ia / product Ib = weight ratio 50/48 / 2.
Product Ia (m = about 12):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product Ib (m = about 12):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
19 F-NMR; δ = 82.0 (3F: C F 3- )
-113.1 (4F: -C F 2 CH 2 C F 2- )
-114.5 (2F: -CF 2 C F 2 CH 2 CH 2- )
-121.9 to -127.0 (10F: -C F 2- )
1 H-NMR; δ = 1.74 (2H: -CF 2 CH 2 C H 2- )
2.25 (2H: -CF 2 C H 2 CH 2- )
2.90 (2H: -CF 2 C H 2 CF 2- )
3.25 (3H: -OC H 3 )
3.20-3.70 (48H: -OC H 2 CH 2 O-, -OCH 2 C H 2 O-)
4.10 (2H: -P (O) OC H 2 CH 2- )
実施例２
実施例１において、前記参考例２(2)で得られたポリフルオロアルキルホスホン酸B 99g(0.20モル)およびPEG-a 201g(0.40モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有18.5重量％)を280g(回収率93％)得た。
Example 2
In Example 1, 99 g (0.20 mol) of the polyfluoroalkylphosphonic acid B obtained in Reference Example 2 (2) and 201 g (0.40 mol) of PEG-a were used, and a light yellow wax-like reaction mixture (in the mixture) F (18.5% by weight) was obtained (280 g, recovery rate 93%).
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-a／生成物II a／生成物II b=重量比50/47/3であった。
生成物II a(m=約12)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物II b(m=約12)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕2
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-a / product II a / product II b = weight ratio 50 / 47/3.
Product II a (m = about 12):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product II b (m = about 12):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
実施例３
実施例１において、前記参考例３(2)で得られたポリフルオロアルキルホスホン酸C 112g(0.19モル)およびPEG-a 188g(0.38モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有21.9重量％)を281g(回収率94％)得た。
Example 3
In Example 1, 112 g (0.19 mol) of polyfluoroalkylphosphonic acid C obtained in Reference Example 3 (2) and 188 g (0.38 mol) of PEG-a were used, and a light yellow wax-like reaction mixture (in the mixture) As a result, 281 g (recovery rate 94%) of F was obtained (21.9% by weight).
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-a／生成物III a／生成物III b=重量比48/48/4であった。
生成物III a(m=約12)：
C2F5(CH2CF2)(CF2CF2)3(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物III b(m=約12)：
C2F5(CH2CF2)(CF2CF2)3(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕2
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-a / product III a / product III b = weight ratio 48 / 48/4.
Product III a (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product III b (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
実施例４
実施例１において、前記参考例４(2)得られたポリフルオロアルキルホスホン酸D 99g(0.20モル)およびPEG-a 201g(0.40モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有18.8重量％)を276g(回収率92％)得た。
Example 4
In Example 1, 99 g (0.20 mol) of polyfluoroalkylphosphonic acid D obtained in Reference Example 4 (2) and 201 g (0.40 mol) of PEG-a were used, and a light yellow wax-like reaction mixture (F in the mixture) was used. As a result, 276 g (recovery rate: 92%) was obtained.
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-a／生成物IV a／生成物IV b=重量比50/47/3であった。
生成物IV a(m=約12)：
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物IV b(m=約12)：
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕2
The resulting reaction mixture was separated by preparative liquid chromatography and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-a / product IV a / product IV b = weight ratio 50 / 47/3.
Product IV a (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product IV b (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
実施例５
実施例１において、前記参考例５(2)で得られたポリフルオロアルキルホスホン酸E 107g(0.19モル)およびPEG-a 193g(0.39モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有18.3重量％)を272g(回収率91％)得た。
Example 5
In Example 1, 107 g (0.19 mol) of polyfluoroalkylphosphonic acid E obtained in the above Reference Example 5 (2) and 193 g (0.39 mol) of PEG-a were used, and a light yellow wax-like reaction mixture (in the mixture) 272 g (recovery rate 91%) of F (18.3 wt%) was obtained.
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-a／生成物Va／生成物Vb=重量比49/48/3であった。
生成物Va(m=約12)：
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物Vb(m=約12)：
C2F5(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)〔O(CH2CH2O)mCH3〕2
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-a / product Va / product Vb = weight ratio 49/48 / 3.
Product Va (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product Vb (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
実施例６
実施例１において、前記参考例６(2)で得られたポリフルオロアルキルホスホン酸F 85g(0.22モル)およびPEG-a 215g(0.43モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有14.9重量％)を274g(回収率91％)得た。
Example 6
In Example 1, 85 g (0.22 mol) of polyfluoroalkylphosphonic acid F obtained in Reference Example 6 (2) and 215 g (0.43 mol) of PEG-a were used, and a light yellow wax-like reaction mixture (in the mixture) 274 g (91% recovery rate) of F (14.9% by weight) was obtained.
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-a／生成物VI a／生成物VI b=重量比49/48/3であった。
生成物VI a(m=約12)：
C2F5(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物VI b(m=約12)：
C2F5(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕2
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-a / product VI a / product VI b = weight ratio 49 / 48/3.
Product VI a (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product VI b (m = about 12):
C 2 F 5 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
実施例７
実施例１において、前記参考例２(2)で得られたポリフルオロアルキルホスホン酸B 60g(0.12モル)およびPEG-a 240g(0.48モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有11.3重量％)を274g(回収率91％)得た。
Example 7
In Example 1, 60 g (0.12 mol) of polyfluoroalkylphosphonic acid B obtained in Reference Example 2 (2) and 240 g (0.48 mol) of PEG-a were used, and a light yellow wax-like reaction mixture (in the mixture) As a result, 274 g (recovery rate: 91%) of F (11.3 wt%) was obtained.
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-a／生成物II a／生成物II b=重量比50/3/47であった。
生成物II a(m=約12)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物II b(m=約12)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕2
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-a / product II a / product II b = weight ratio 50 / 3/47.
Product II a (m = about 12):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product II b (m = about 12):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
実施例８
実施例１において、前記参考例２(2)で得られたポリフルオロアルキルホスホン酸B 35g(0.07モル)およびポリエチレングリコールモノメチルエーテル〔PEG-b〕(日油製品ユニオックスM-2000；MW=1816、m=約45)
HO(CH2CH2O)mCH3
265g(0.15モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有6.6重量％)を280g(回収率93％)得た。
Example 8
In Example 1, 35 g (0.07 mol) of polyfluoroalkylphosphonic acid B obtained in Reference Example 2 (2) and polyethylene glycol monomethyl ether [PEG-b] (Nippon Oil Products UNIOX M-2000; MW = 1816) , M = about 45)
HO (CH 2 CH 2 O) m CH 3
Using 265 g (0.15 mol), 280 g (recovery rate: 93%) of a pale yellow wax-like reaction mixture (6.6% by weight of F in the mixture) was obtained.
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PEG-b／生成物VII a／生成物VII b=重量比48/48/4であった。
生成物VII a(m=約45)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕(OH)
生成物VII b(m=約45)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O)〔O(CH2CH2O)mCH3〕2
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PEG-b / product VII a / product VII b = weight ratio 48 / 48/4.
Product VII a (m = about 45):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) (OH)
Product VII b (m = about 45):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) (O (CH 2 CH 2 O) m CH 3 ) 2
実施例９
実施例１において、前記参考例２(2)で得られたポリフルオロアルキルホスホン酸B 75g(0.15モル)およびポリプロピレングリコールモノブチルエーテル〔PPG-a〕(三洋化成製品ニューポールM-30；MW=786、m=約14)
HO〔CH2CH(CH3)O〕mC4H9
225g(0.29モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有14.0重量％)を280g(回収率93％)得た。
Example 9
In Example 1, 75 g (0.15 mol) of polyfluoroalkylphosphonic acid B obtained in Reference Example 2 (2) and polypropylene glycol monobutyl ether [PPG-a] (Sanyo Chemicals New Pole M-30; MW = 786) , M = about 14)
HO [CH 2 CH (CH 3 ) O] m C 4 H 9
Using 225 g (0.29 mol), 280 g (recovery rate: 93%) of a pale yellow wax-like reaction mixture (14.0% by weight of F in the mixture) was obtained.
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PPG-a／生成物VIII a／生成物VIII b=重量比48/49/3であった。
生成物VIII a(m=約14)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O){O〔CH2CH(CH3)O〕mC4H9}(OH)
生成物VIII b(m=約14)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O){O〔CH2CH(CH3)O〕mC4H9}2
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PPG-a / product VIII a / product VIII b = weight ratio 48 / 49/3.
Product VIII a (m = about 14):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) {O [CH 2 CH (CH 3 ) O] m C 4 H 9 } (OH)
Product VIII b (m = about 14):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) {O [CH 2 CH (CH 3 ) O] m C 4 H 9 } 2
実施例１０
実施例１において、前記参考例２(2)で得られたポリフルオロアルキルホスホン酸B 122g(0.22モル)およびポリプロピレングリコール〔PPG-b〕(日油製品ユニオックスD-400；MW=418、m=約8)
HO〔CH2CH(CH3)O〕mH
178g(0.43モル)を用い、淡黄色ワックス状の反応混合物(混合物中のF含有22.6重量％)を281g(回収率94％)得た。
Example 10
In Example 1, 122 g (0.22 mol) of polyfluoroalkylphosphonic acid B obtained in Reference Example 2 (2) and polypropylene glycol [PPG-b] (Nippon Oil Products UNIOX D-400; MW = 418, m = Approx. 8)
HO [CH 2 CH (CH 3 ) O] m H
Using 178 g (0.43 mol), 281 g (94% recovery rate) of a pale yellow wax-like reaction mixture (22.6% by weight of F in the mixture) was obtained.
得られた反応混合物を分取液体クロマトグラフィーで分離し、分離物の組成を19F-NMRおよび1H-NMRによって確認すると、PPG-b／生成物IX a／生成物IX b／生成物IX c=重量比48/46/3/3であった。
生成物IX a(m=約8)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O){O〔CH2CH(CH3)O〕mH}(OH)
生成物IX b(m=約8)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)P(O){O〔CH2CH(CH3)O〕mH}2
生成物IX c(m=約8)：
C4F9(CH2CF2)(CF2CF2)(CH2CH2)-P(O)(OH)-O〔CH2CH(CH3)O〕m-P(O)(OH)-
(CH2CH2)(CF2CF2)(CF2CH2)C4F9
The resulting reaction mixture was separated by preparative liquid chromatography, and the composition of the separation was confirmed by 19 F-NMR and 1 H-NMR. PPG-b / product IX a / product IX b / product IX c = weight ratio 48/46/3/3.
Product IX a (m = about 8):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) {O [CH 2 CH (CH 3 ) O] m H} (OH)
Product IX b (m = about 8):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) P (O) {O [CH 2 CH (CH 3 ) O] m H} 2
Product IX c (m = about 8):
C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) -P (O) (OH) -O [CH 2 CH (CH 3 ) O] m -P (O) (OH )-
(CH 2 CH 2 ) (CF 2 CF 2 ) (CF 2 CH 2 ) C 4 F 9
参考例７
実施例１で得られたポリフルオロアルキルホスホン酸オキシアルキレンエステル(生成物Ib)0.5重量部をイオン交換水99.5重量部に添加し、離型剤水溶液を調製した。この離型剤水溶液を用いて、次のような2種類の測定方法で離型性の評価を行うと、金型離型性評価では6Nであり、離型寿命評価は10回であった。
Reference Example 7
0.5 part by weight of the polyfluoroalkylphosphonic acid oxyalkylene ester (product Ib) obtained in Example 1 was added to 99.5 parts by weight of ion-exchanged water to prepare an aqueous release agent solution. When this release agent aqueous solution was used to evaluate the releasability by the following two types of measurement methods, the mold releasability evaluation was 6N, and the release life evaluation was 10 times.
＜金型離型性および寿命評価＞
80℃に加熱されたポリウレタンプレポリマー(日本ポリウレタン工業製品コロネートC-4090)100重量部と加熱溶融されたメチレンビス-o-クロロアニリン硬化剤(イハラケミカル製品イハラキュアミンMT)12.8重量部とを、気泡を巻き込まないようにしながら攪拌混合し、この混合物を80℃に予熱された上記離型剤水溶液スプレー塗布アルミニウム製金型(直径45mm、深さ50mm)内に注入する。金型空間部中央に、硬化した成形品を取出すためのフックを立てておき、120℃で1時間加熱硬化させた後、フックを引張って成形品を金型から取出す。この際の離型荷重を金型離型性とした。また、このようにして金型離型性を求めた後、1回の離型剤水溶液塗布で、49N以下の離型荷重条件下で、何回迄離型が可能であったかを測定し、金型寿命とした。
<Evaluation of mold releasability and life>
100 parts by weight of polyurethane prepolymer heated to 80 ° C. (Japan Polyurethane Industrial Product Coronate C-4090) and 12.8 parts by weight of heat-melted methylenebis-o-chloroaniline curing agent (Ihara Chemical product Iharacamine MT), The mixture is stirred and mixed so as not to entrain air bubbles, and the mixture is poured into the above-mentioned mold release agent spray-coated aluminum mold (diameter 45 mm, depth 50 mm) preheated to 80 ° C. At the center of the mold space, a hook for taking out the cured molded product is set up, and after being cured by heating at 120 ° C. for 1 hour, the hook is pulled to remove the molded product from the mold. The mold release load at this time was defined as mold releasability. In addition, after determining mold releasability in this way, it was measured how many times mold release was possible under a release load condition of 49 N or less with one application of a release agent aqueous solution. The mold life was assumed.
Claims (2)
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)〔O(RO)mR′〕d(OH)2-d
(ここで、ROは炭素数2〜6の直鎖状または分岐状オキシアルキレン基であり、R′は水素原子または炭素数1〜20のアルキル基またはアラルキル基であり、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、mは1〜100の整数、dは1または2である)で表わされるポリフルオロアルキルホスホン酸オキシアルキレンエステル。 General formula
C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) [O (RO) m R ′] d (OH) 2-d
(Wherein RO is a linear or branched oxyalkylene group having 2 to 6 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and n is 1 to 6 carbon atoms. An integer of 1 to 4, b is an integer of 1 to 3, c is an integer of 1 to 3, m is an integer of 1 to 100, and d is 1 or 2. Oxyalkylene ester.
CC nn FF 2n+12n + 1 (CH(CH 22 CFCF 22 )) aa (CF(CF 22 CFCF 22 )) bb (CH(CH 22 CHCH 22 )) cc P(O)(OH)P (O) (OH) 22
(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と一般式(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) and a general formula
HO(RO)HO (RO) mm R′R ′
(ここで、ROは炭素数2〜6の直鎖状または分岐状オキシアルキレン基であり、R′は水素原子または炭素数1〜20のアルキル基またはアラルキル基であり、mは1〜100の整数である)で表わされるポリアルキレングリコールまたはそのモノエーテルとを縮合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オキシアルキレンエステルの製造法。(Wherein RO is a linear or branched oxyalkylene group having 2 to 6 carbon atoms, R ′ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and m is 1 to 100. 2. The method for producing a polyfluoroalkylphosphonic acid oxyalkylene ester according to claim 1, wherein the polyalkylene glycol represented by the formula (1) is a condensation reaction with a monoether thereof.
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| JP2009210289A JP4711011B2 (en) | 2009-09-11 | 2009-09-11 | Polyfluoroalkylphosphonic acid oxyalkylene ester and process for producing the same |
| EP10815370.1A EP2476687B1 (en) | 2009-09-11 | 2010-09-08 | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing same and release agent containing same as active ingredient |
| PCT/JP2010/065383 WO2011030775A1 (en) | 2009-09-11 | 2010-09-08 | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing same and release agent containing same as active ingredient |
| KR1020127006226A KR101396183B1 (en) | 2009-09-11 | 2010-09-08 | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing same and release agent containing same as active ingredient |
| US13/395,186 US8377188B2 (en) | 2009-09-11 | 2010-09-08 | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing the same, and mold-releasing agent comprising the same as active ingredient |
| CN201080040658.5A CN102574880B (en) | 2009-09-11 | 2010-09-08 | Polyfluoroalkylphosphonic acid oxyalkylene ester, method for producing same and release agent containing same as active ingredient |
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| JPS59166596A (en) * | 1983-03-14 | 1984-09-19 | Nippon Mektron Ltd | Mold release agent |
| JPS60190309A (en) * | 1984-03-12 | 1985-09-27 | Nippon Mektron Ltd | Releasing agent |
| US5846516A (en) * | 1992-06-03 | 1998-12-08 | Alliance Pharmaceutial Corp. | Perfluoroalkylated amphiphilic phosphorus compounds: preparation and biomedical applications |
| JP2872065B2 (en) * | 1995-01-26 | 1999-03-17 | 日本メクトロン株式会社 | Acrylic elastomer composition and vulcanized molded article thereof |
| CA2643067C (en) * | 2006-03-10 | 2012-06-19 | Unimatec Co., Ltd. | Polyfluoroalkyl alcohol, or (meth)acrylic acid derivative thereof, and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137798A (en) * | 2015-10-09 | 2018-06-08 | 信越化学工业株式会社 | Polymer modification phosphonate derivative containing fluoro alkylidene oxide and the surface conditioning agent containing the derivative and the surface treatment method using the surface conditioning agent |
| CN108137798B (en) * | 2015-10-09 | 2020-06-09 | 信越化学工业株式会社 | Polymer-modified phosphonic acid derivative containing fluorinated oxyalkylene group, and corresponding surface treatment agent and surface treatment method |
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| JP2011057632A (en) | 2011-03-24 |
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