JPH02286690A - Purification of phosphoric ester - Google Patents
Purification of phosphoric esterInfo
- Publication number
- JPH02286690A JPH02286690A JP10681189A JP10681189A JPH02286690A JP H02286690 A JPH02286690 A JP H02286690A JP 10681189 A JP10681189 A JP 10681189A JP 10681189 A JP10681189 A JP 10681189A JP H02286690 A JPH02286690 A JP H02286690A
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- mol
- solvents
- diester
- monoester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000746 purification Methods 0.000 title claims description 3
- 150000002148 esters Chemical class 0.000 title abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 150000005690 diesters Chemical class 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000005456 alcohol based solvent Substances 0.000 claims abstract description 4
- 239000003759 ester based solvent Substances 0.000 claims abstract description 4
- 239000005453 ketone based solvent Substances 0.000 claims abstract description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 17
- 238000001640 fractional crystallisation Methods 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- JTXUVYOABGUBMX-UHFFFAOYSA-N didodecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCC JTXUVYOABGUBMX-UHFFFAOYSA-N 0.000 description 7
- FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 6
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- RNPXCFINMKSQPQ-UHFFFAOYSA-N dicetyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCC RNPXCFINMKSQPQ-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- -1 pyrophosphoric acid ester Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- XQZPQRQQSHJDGK-UHFFFAOYSA-N dihexadecyl phosphono phosphate Chemical compound CCCCCCCCCCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCCCCCCCCCC XQZPQRQQSHJDGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- QHAUASBJFFBWMY-UHFFFAOYSA-N didecyl hydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(=O)OCCCCCCCCCC QHAUASBJFFBWMY-UHFFFAOYSA-N 0.000 description 1
- AQNVYUAYYQMVCF-UHFFFAOYSA-N didodecyl phosphono phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCCCCCC AQNVYUAYYQMVCF-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- ORLWXEYHGUZEHI-UHFFFAOYSA-N dioctadecyl phosphono phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCCCCCCCCCCCC ORLWXEYHGUZEHI-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野コ 本発明はリン酸エステルの精製法に関する。[Detailed description of the invention] [Industrial application fields] The present invention relates to a method for purifying phosphoric acid esters.
［従来の技術］
従来、リン酸エステルの精製法としてモノエステルおよ
びジエステルを高純度に得る方法としては、粗製リン酸
エステルをアルカリまたはアミン存在下で液状炭化水素
および水（場合によりアルコールを含む）の混合液で抽
出分離する技術がある（例えば 油化学 第１６巻 第
７号 ｐ、３２〜３３（１９６７）、特開昭ＧＯ−２５
８１９１号公報）。[Prior Art] Conventionally, as a method for purifying phosphoric acid esters to obtain monoesters and diesters with high purity, crude phosphoric acid esters are treated with liquid hydrocarbons and water (including alcohol in some cases) in the presence of an alkali or amine. There is a technique for extraction and separation using a mixed liquid of
Publication No. 8191).
［発明が解決しようとする課題］
しかしこの技術では、アルカリまたはアミン水溶液およ
び酸水溶液等で繰り返し抽出する必要があり、大量の廃
水が出る、操作が煩雑であるなどの問題がある。[Problems to be Solved by the Invention] However, this technique requires repeated extraction with an alkali or amine aqueous solution, an acid aqueous solution, etc., and there are problems such as a large amount of waste water being produced and the operation being complicated.
［課題を解決するための手段］
本発明者らは、アルカリまたはアミン水溶液および酸水
溶液等で繰り返し抽出する必要がなく、大量の廃水が出
ず、操作が簡単なリン酸エステルの精製法について鋭意
検討した結果、本発明に到達した。[Means for Solving the Problems] The present inventors have worked hard to develop a method for purifying phosphoric acid esters that does not require repeated extraction with alkali or amine aqueous solutions and acid aqueous solutions, does not generate large amounts of waste water, and is easy to operate. As a result of study, we have arrived at the present invention.
すなわち本発明は、モノエステルとジエステルの混合物
（モノエステル１〜９０モル％、ジエスチル１０〜９９
モル％）を主成分とする粗製リン酸エステルを、溶剤で
分別結晶してモノエステルを母液側に、ジエステルを沈
澱側に分離することによって高純度のモノエステルおよ
び高純度のジエステルを同時に得ることを特徴とするリ
ン酸エステルの精製法である。That is, the present invention provides a mixture of monoester and diester (monoester 1 to 90 mol%, diethyl 10 to 99 mol%).
A crude phosphoric acid ester whose main component is mol%) is fractionally crystallized in a solvent to separate the monoester into the mother liquor side and the diester into the precipitate side, thereby simultaneously obtaining a high-purity monoester and a high-purity diester. This is a method for purifying phosphoric acid esters.
モノエステルとジエステルの混合物を主成分とする粗製
リン酸エステルとしては、炭素数６以上のアルコールの
リン酸モノエステルまたはジエステル例えば、モノまた
はジオクチルリン酸、モノまたはジデシルリン酸、モノ
またはジドデシルリン酸、モノまたはジオクタデシルリ
ン酸、モノまたはジオクチニルリン酸、モノまたはジオ
クタデシルリン酸、モノまたはジオクチニルリン酸、モ
ノまたはジオクタデセニルリン酸、モノまたはジテトラ
コセニルリン酸、モノまたはジ２−へキシルデシルリン
酸、モノまたはジ２−オクチルウンデシルリン酸、モノ
またはジ２−テトラデシルオクタデシルリン酸等が挙げ
られる。Crude phosphoric acid esters mainly composed of a mixture of monoester and diester include phosphoric acid monoesters or diesters of alcohols having 6 or more carbon atoms, such as mono- or dioctyl phosphoric acid, mono- or didecyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphate, mono or dioctinyl phosphate, mono or dioctadecyl phosphate, mono or dioctinyl phosphate, mono or dioctadecenyl phosphate, mono or ditetracosenyl phosphate, mono or di-2-hexyldecyl phosphate acids, mono- or di-2-octyl undecyl phosphoric acid, mono- or di-2-tetradecyl octadecyl phosphoric acid, and the like.
粗製リン酸エステルは通常、アルコールと無水リン酸を
反応させて得られる。その組成は通常、モノエステルが
２５〜７５モル％、ジエステルが５〜５０モル％、オル
トリン酸が１〜２５モ／Ｌ／％、ピロリン酸エステルが
０〜３０モル％を有する。Crude phosphoric acid esters are usually obtained by reacting alcohol with phosphoric anhydride. Its composition usually has 25 to 75 mol% of monoester, 5 to 50 mol% of diester, 1 to 25 mol/L/% of orthophosphoric acid, and 0 to 30 mol% of pyrophosphoric acid ester.
この粗製物を溶剤で分別結晶する。This crude product is fractionally crystallized using a solvent.
溶剤としては、ケトン系溶剤（炭素数３〜６のケトン例
えばアセトン、メチルエチルケトン、メチルイソブチル
ケトン等）、アルコール系溶剤（炭素数１〜４の脂肪族
アルコール例えばメタノール、エタノール、イソプロパ
ツール、ｎ−ブタノール等、炭素数６〜１０の芳香族ア
ルコール例えばベンジルアルコール等、炭素数６〜１２
の支環式アルコール例えばシクロヘキサノール等、セル
ソルブ系溶剤例えばエチルセルソルブ、ブチルセルソル
ブ等）、エステル系溶剤（炭素数１〜５のエステル例え
ば酢酸メチル、酢酸エチル、プロピオン酸エチル等）、
エーテル系溶剤（ジメチルエーテル、エチルメチルエー
テル、ジエチルエーテル、テトラヒドロフラン等）、炭
化水素系溶剤（ｎ−ヘキサン、シクロヘキサン、ベンゼ
ン、トルエン、キシレン等）ハロゲン系溶剤（四塩化炭
素、ジクロロエタン、１． ２−ジクロロエタン、クロ
ロベンゼン等）、アミド系溶剤（ジメチルホルムアミド
、ジエチルホルムアミド等）、スルホキシド系溶剤（ジ
メチルスルホキシド、ジエチルスルホキシド等）および
これらの２種以上の混合物が挙げられる。好ましいのは
ケトン系溶剤、アルコール系溶剤およびエステル系溶剤
である。特に好ましいのはアセトン、メタノールおよび
酢酸エチルである。溶剤には必要により水を含有または
併用してもよい。その場合水の量は溶剤と水の合計重量
中で通常５０％以下好ましくは１０％以下である。Examples of solvents include ketone solvents (ketones having 3 to 6 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, isopropanol, n- Aromatic alcohol with 6 to 10 carbon atoms such as butanol, 6 to 12 carbon atoms such as benzyl alcohol
cyclic alcohols such as cyclohexanol, cellosolve solvents such as ethyl cellosolve, butyl cellosolve, etc.), ester solvents (esters having 1 to 5 carbon atoms, such as methyl acetate, ethyl acetate, ethyl propionate, etc.),
Ether solvents (dimethyl ether, ethyl methyl ether, diethyl ether, tetrahydrofuran, etc.), hydrocarbon solvents (n-hexane, cyclohexane, benzene, toluene, xylene, etc.), halogen solvents (carbon tetrachloride, dichloroethane, 1.2-dichloroethane) , chlorobenzene, etc.), amide solvents (dimethylformamide, diethylformamide, etc.), sulfoxide solvents (dimethylsulfoxide, diethylsulfoxide, etc.), and mixtures of two or more thereof. Preferred are ketone solvents, alcohol solvents and ester solvents. Particularly preferred are acetone, methanol and ethyl acetate. The solvent may contain water or be used in combination with it, if necessary. In that case, the amount of water is usually 50% or less, preferably 10% or less based on the total weight of the solvent and water.
溶剤の量は通常粗製リン酸エステルの通常３倍以上好ま
しくは５〜２０倍である。The amount of solvent is usually 3 times or more, preferably 5 to 20 times the amount of the crude phosphoric ester.
分別結晶は粗製リン酸エステルを温溶剤に溶かし、必要
により濾過後、常温以下に冷却する。温溶剤の温度は粗
製リン酸エステルが溶ける温度でよい。For fractional crystallization, the crude phosphoric acid ester is dissolved in a warm solvent, filtered if necessary, and then cooled to below room temperature. The temperature of the hot solvent may be a temperature at which the crude phosphoric acid ester is dissolved.
濾過方法は濾紙、グラスフィルター フィルタープレス
等を用いる。The filtration method uses filter paper, glass filter, filter press, etc.
冷却は常温以下、場合によっては冷蔵庫等て０°Ｃ以下
にする。Cool to room temperature or below, or in some cases, use a refrigerator to cool to below 0°C.
分別結晶の回数は特に制限されず、１回でも２回以上で
もよい。分別結晶を２回以上行う場合、溶剤は同じでも
異なってもよい。The number of times of fractional crystallization is not particularly limited, and may be performed once or twice or more. When fractional crystallization is performed more than once, the solvents may be the same or different.
分別結晶で沈澱と母液が得られる。沈澱の方は、ジエス
テルが主成分で（通常９０モル％以上）更に再結晶を行
うことによって更に高純度のジエステルが得られる。再
結晶の方法は分別結晶と同じでよい。母液の方は、溶剤
を蒸留によって回収することにより、モノエステルが主
成分の残 が得られる（通常７０モル％以上）。これを
更に再結晶することにより、更に高純度のモノエステル
が得られる。再結晶の方法は分別結晶と同じでよい。Precipitate and mother liquor are obtained by fractional crystallization. In the case of precipitation, diester is the main component (usually 90 mol % or more), and by further recrystallization, higher purity diester can be obtained. The method of recrystallization may be the same as that for fractional crystallization. By recovering the solvent from the mother liquor by distillation, a residue consisting mainly of monoester can be obtained (usually 70 mol% or more). By further recrystallizing this, a monoester with even higher purity can be obtained. The method of recrystallization may be the same as that for fractional crystallization.
本発明の方法では１００％ジエステル、１００％モノエ
ステルが得られる。The method of the present invention yields 100% diester and 100% monoester.
本発明の方法で作られるリン酸エステルはすべて酸の形
で得られるが必要によってアルカリまたはアミンで中和
すれば塩にすることが出来る。All of the phosphoric acid esters produced by the method of the present invention are obtained in the form of acids, but if necessary, they can be made into salts by neutralization with an alkali or amine.
［実施例コ
以下、実施例により本発明を説明するが、本発明はこれ
に限定されるものではない。[Example] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
モノラウリルリン酸５０モル％、ジラウリルリン酸４６
モル％、オルトリン酸３モル％、ジラウリルピロリン酸
１モル％からなる粗製リン酸エステル１００．０ｇを攪
拌器および還流管を備えた反応槽に入れた後、アセトン
１０１００Ｏを加え、５０″Ｃで３０分攪拌し、完全に
溶解させた。その後５℃で５時間静置し、析出した沈澱
をグラスフィルターで濾過した。沈澱は、０°Ｃのアセ
トン１０ｍ１で洗浄した後、真空デシケータ−で乾燥し
、次の分析値を持つジラウリルリン酸８１．０ｇを得た
。Example 1 50 mol% monolauryl phosphoric acid, 46 mol% dilauryl phosphoric acid
After putting 100.0 g of a crude phosphoric acid ester consisting of 3 mol% of orthophosphoric acid and 1 mol% of dilauryl pyrophosphoric acid into a reaction tank equipped with a stirrer and a reflux tube, 10,100 O of acetone was added, and the mixture was heated at 50''C. The mixture was stirred for 30 minutes to completely dissolve.Then, it was allowed to stand at 5°C for 5 hours, and the precipitate was filtered with a glass filter.The precipitate was washed with 10ml of acetone at 0°C, and then dried in a vacuum desiccator. 81.0 g of dilauryl phosphoric acid having the following analytical values was obtained.
モノラウリルリン酸 ４モル％ジラウリルリン
酸 ９６モル％このジラウリルリン酸をアセト
ンにより再結晶することにより、１００％ジラウリルリ
ン酸が得られた。Monolauryl phosphoric acid 4 mol% dilauryl phosphoric acid 96 mol% By recrystallizing this dilauryl phosphoric acid with acetone, 100% dilauryl phosphoric acid was obtained.
分別結晶母液を蒸留によりアセトンを回収した後真空で
脱アセトンすることにより、次の分析値を持つモノラウ
リルリン酸３０．７ｇを得た。Acetone was recovered from the fractionated crystal mother liquor by distillation, and then deacetone was removed in vacuo to obtain 30.7 g of monolauryl phosphoric acid having the following analytical values.
モノラウリルリン酸 ８９モル％ジラウリルリン
酸 １モル％オルトリン酸
８モル％ジラウリルビロリン酸 ２モル％このモ
ノラウリルリン酸をｎ−ヘキサンにより再結晶すること
により、１００％モノラウリルリン酸が得られた。Monolauryl phosphoric acid 89 mol% dilauryl phosphoric acid 1 mol% orthophosphoric acid
8 mol% dilauryl birophosphoric acid 2 mol% This monolauryl phosphoric acid was recrystallized from n-hexane to obtain 100% monolauryl phosphoric acid.
この分析は重クロロホルム中で２ＩＰ−ＮＭＲスペクト
ルを測定することにより決定した。以後の実施例に於て
も同様の分析法を用いた。This analysis was determined by measuring 2IP-NMR spectra in deuterated chloroform. Similar analytical methods were used in subsequent examples.
実施例２
モノセチルリン酸４８モル％、ジセチルリン酸４８モル
％、オルトリン酸３モル％、ジセチルピロリン酸１モル
％からなる粗製リン酸エステル５０．０ｇを攪拌器およ
び還流管を備えた反応槽に入れた後、メタノール５００
ｍ１を加え、６０℃で３０分攪拌し、完全に溶解させた
。その後１０℃で５時間静置し、析出した沈澱をグラス
フィルターで濾過した。沈澱は、１０°Ｃのメタノール
１０ｍ１で洗浄した後、真空デシケータ−で乾燥し、次
の分析値を持つジセチルリン酸３４．１ｇを得た。Example 2 50.0 g of a crude phosphoric acid ester consisting of 48 mol% monocetyl phosphoric acid, 48 mol% dicetyl phosphoric acid, 3 mol% orthophosphoric acid, and 1 mol% dicetyl pyrophosphoric acid was placed in a reaction tank equipped with a stirrer and a reflux tube. After that, methanol 500
m1 was added and stirred at 60°C for 30 minutes to completely dissolve. Thereafter, the mixture was allowed to stand at 10° C. for 5 hours, and the precipitate deposited was filtered using a glass filter. The precipitate was washed with 10 ml of methanol at 10°C and then dried in a vacuum desiccator to obtain 34.1 g of dicetyl phosphoric acid having the following analytical values.
モノセチルリン酸 ７モノステアルリン酸
９３モル％
このジセチルリン酸をメタノールにより再結晶すること
により、１００％ジセチルリン酸が得られた。Monocetyl phosphoric acid 7-monostearic acid
By recrystallizing this 93 mol% dicetyl phosphoric acid with methanol, 100% dicetyl phosphoric acid was obtained.
分別結晶母液を蒸留によりメタノールを回収した後真空
で脱メタノールすることにより次の分析値を持つモノセ
チルリン酸１４．８ｇを得た。Methanol was recovered from the fractionated crystal mother liquor by distillation, and then methanol was removed in vacuo to obtain 14.8 g of monocetyl phosphoric acid having the following analytical values.
モノセチルリン酸 ９０モモノステアルリン酸
１モル％
オルトリン酸 ７モル％ジセチルピロリ
ン酸 ２モル％このモノセチルリン酸をｎ−ヘ
キサンにより再結晶することにより、１００％モノセチ
ルリン酸が得られた。Monocetyl phosphoric acid 90 Monostearic acid 1 mol% Orthophosphoric acid 7 mol% Dicetyl pyrophosphoric acid 2 mol% By recrystallizing this monocetyl phosphoric acid from n-hexane, 100% monocetyl phosphoric acid was obtained.
実施例３
モノステアリルリン酸４６モル％、ジステアリルリン酸
４４モル％、オルトリン酸３モル％、ジステアルビロリ
ン酸７モル％からなる組成リン酸エステル５０．０ｇを
攪拌器および還流管を備えた反応槽に入れた後、酢酸エ
チル５００ｍ１を加え、７０℃で３０分攪拌し、完全に
溶解させた。Example 3 Composition consisting of 46 mol% of monostearyl phosphoric acid, 44 mol% of distearyl phosphoric acid, 3 mol% of orthophosphoric acid, and 7 mol% of distealbirophosphoric acid 50.0 g of phosphoric acid ester was prepared using a stirrer and reflux tube. Then, 500 ml of ethyl acetate was added and stirred at 70°C for 30 minutes to completely dissolve the mixture.
その後１０℃で５時間静置し、析出した沈澱をグラスフ
ィルターで濾過した。沈澱は、１０℃の酢酸エチル１０
ｍ１で洗浄した後、真空デシケータ−で乾燥し、次の分
析値を持つジステアリン酸３７．３ｇを得た。Thereafter, the mixture was allowed to stand at 10° C. for 5 hours, and the precipitate deposited was filtered using a glass filter. Precipitate in ethyl acetate at 10°C.
After washing with m1, it was dried in a vacuum desiccator to obtain 37.3 g of distearic acid having the following analytical values.
モノステアルリン酸 １２モル％ジステアルリン
酸 ８８モル％このジステアリルリン酸を酢酸
エチルにより再結晶を２回することにより、１００％ジ
ステアリルリン酸が得られた。Monostearyl phosphoric acid 12 mol% Distearyl phosphoric acid 88 mol% This distearyl phosphoric acid was recrystallized twice from ethyl acetate to obtain 100% distearyl phosphoric acid.
分別結晶母液を蒸留により酢酸エチルを回収した後真空
で脱酢酸エチルすることにより次の分析値を持つモノス
テアリルリン酸１０．２ｇを得た。Ethyl acetate was recovered from the fractionated crystal mother liquor by distillation, and then ethyl acetate was removed in vacuo to obtain 10.2 g of monostearyl phosphoric acid having the following analytical values.
モノステアリルリン酸 ７４モル％ジステアリルリ
ン酸 ２モル％オルトリン酸
８モル％ジステアリルピロリン酸 １６モル％このモ
ノステアリルリン酸をｎ−ヘキサンにより再結晶するこ
とにより、１００％モノステアリルリン酸が得られた。Monostearyl phosphoric acid 74 mol% distearyl phosphoric acid 2 mol% orthophosphoric acid
8 mol% distearyl pyrophosphate 16 mol% This monostearyl phosphoric acid was recrystallized from n-hexane to obtain 100% monostearyl phosphoric acid.
［発明の効果］
本発明の方法は、アミンまたはアルカリ水溶液および酸
水溶液等で繰り返し抽出する必要がなく、大量の廃水が
出す、操作が簡単という効果を奏する。[Effects of the Invention] The method of the present invention has the advantage that there is no need for repeated extractions with amine or alkaline aqueous solutions, acid aqueous solutions, etc., a large amount of waste water is produced, and the operation is simple.
■ 高純度のモノエステルと高純度のジエステルが同時
に得られる。■ High purity monoester and high purity diester can be obtained at the same time.
■ 使われた溶剤を回収できる。■ The used solvent can be recovered.
■ 収率がよい。■ Good yield.
■ 酸の形で取れるために中和度を自由に変えることが
出来る。■ Since it is obtained in acid form, the degree of neutralization can be changed freely.
上記の効果を奏することから本発明の方法で得られるリ
ン酸エステル（モノエステル、ジエステル）は高純度で
あることが必要な香粧品用基剤、有価金属の回収精製剤
に特にを効である。また、繊維用処理剤、乳化剤、防錆
剤等にも利用できる。Because of the above-mentioned effects, the phosphoric acid esters (monoesters, diesters) obtained by the method of the present invention are particularly effective as bases for cosmetics and valuable metal recovery and purification agents that require high purity. . It can also be used as a treatment agent for textiles, an emulsifier, a rust preventive agent, etc.
Claims (1)
１〜９０モル％、ジエステル１０〜９９モル％）を主成
分とする粗製リン酸エステルを、溶剤で分別結晶してモ
ノエステルを母液側に、ジエステルを沈澱側に分離する
ことによって高純度のモノエステルおよび高純度のジエ
ステルを同時に得ることを特徴とするリン酸エステルの
精製法。 ２、溶剤がケトン系溶剤、アルコール系溶剤、エステル
系溶剤、エーテル系溶剤、アミド系溶剤、炭化水素系溶
剤、ハロゲン系溶剤、およびスルホキシド系溶剤からな
る群より選ばれる溶剤である請求項１記載の精製法。[Claims] 1. A crude phosphoric acid ester whose main component is a mixture of monoester and diester (1 to 90 mol% of monoester, 10 to 99 mol% of diester) is fractionally crystallized in a solvent to obtain a monoester. 1. A method for purifying phosphoric acid ester, which is characterized in that a high-purity monoester and a high-purity diester are simultaneously obtained by separating the diester into the mother liquor side and the diester into the precipitate side. 2. The solvent is a solvent selected from the group consisting of ketone solvents, alcohol solvents, ester solvents, ether solvents, amide solvents, hydrocarbon solvents, halogen solvents, and sulfoxide solvents. Purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10681189A JPH02286690A (en) | 1989-04-26 | 1989-04-26 | Purification of phosphoric ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10681189A JPH02286690A (en) | 1989-04-26 | 1989-04-26 | Purification of phosphoric ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02286690A true JPH02286690A (en) | 1990-11-26 |
Family
ID=14443227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10681189A Pending JPH02286690A (en) | 1989-04-26 | 1989-04-26 | Purification of phosphoric ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02286690A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019252A1 (en) * | 1997-10-09 | 1999-04-22 | Monsanto Co | Method for separating phosphorus oxyacids, organophosphates and organophosphites |
-
1989
- 1989-04-26 JP JP10681189A patent/JPH02286690A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019252A1 (en) * | 1997-10-09 | 1999-04-22 | Monsanto Co | Method for separating phosphorus oxyacids, organophosphates and organophosphites |
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