JPH0566958B2 - - Google Patents
Info
- Publication number
- JPH0566958B2 JPH0566958B2 JP17393485A JP17393485A JPH0566958B2 JP H0566958 B2 JPH0566958 B2 JP H0566958B2 JP 17393485 A JP17393485 A JP 17393485A JP 17393485 A JP17393485 A JP 17393485A JP H0566958 B2 JPH0566958 B2 JP H0566958B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphoric acid
- reaction
- alcohol
- acid ester
- 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.)
- Expired - Fee Related
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 69
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 40
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 35
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- -1 aliphatic alcohols Chemical class 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 9
- 150000005690 diesters Chemical class 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000003599 detergent Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical group CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 6
- 150000002440 hydroxy compounds Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000002453 shampoo Substances 0.000 description 4
- 238000010793 Steam injection (oil industry) Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 230000000865 phosphorylative effect Effects 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000021323 fish oil Nutrition 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XGFDHKJUZCCPKQ-UHFFFAOYSA-N nonadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCO XGFDHKJUZCCPKQ-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- SMYREFDDLSTNKQ-UHFFFAOYSA-N oxocan-2-ol Chemical compound OC1CCCCCCO1 SMYREFDDLSTNKQ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
〔産業上の利用分野〕
本発明はリン酸モノエステル含量の多いリン酸
エステルの製造方法に関する。さらに詳しくはリ
ン酸モノエステル含量の多いリン酸エステルを容
易に製造でき、かつ得られるリン酸エステルの色
相、臭気等が良好なリン酸エステルの製造方法に
関するものである。
〔従来の技術〕
有機ヒドロキシ化合物をリン酸化して得られる
リン酸エステルは洗浄剤、乳化剤、繊維処理剤、
帯電防止剤、潤滑油添加剤、防錆剤、医薬品等に
広く用いられている。
通常リン酸化剤に五酸化リンを用い、有機ヒド
ロキシ化合物にリン酸エステル化反応を行なうと
リン酸モノエステルとリン酸ジエステルのほぼ等
モル混合物が得られる。
リン酸モノエステルとリン酸ジエステルとは性
能上大きく異なり、リン酸モノエステルが良好な
水溶性、起泡力、洗浄力を有するのに比べ、リン
酸ジエステルはこれら諸能力が劣つている。
すなわち洗浄剤、シヤンプー等に用いるリン酸
エステルとしてはリン酸モノエステル含量の多い
ものが望まれている。従来、リン酸モノエステル
含量の多いリン酸エステルを製造する方法は種々
提案されているが、水の存在下にリン酸エステル
化反応を行なう方法として、(1)有機ヒドロキシ化
合物に水を添加し、ついで無水リン酸を添加反応
する方法（特公昭41−14416）、(2)有機ヒドロキシ
化合物と水とリン酸化剤とを反応してこの生成物
にさらに有機ヒドロキシ化合物を加えて反応する
方法（特開昭56−86191）等がある。
〔発明が解決しようとする問題点〕
しかしながら(1)の方法は無水リン酸の反応率が
悪く、オルソリン酸が多量に生成し製品に混入す
る等の欠点を有し、(2)の方法はリン酸分が過剰の
状態でリン酸エステル化反応を行なう第１工程と
さらにこの生成物に化学量論量の有機ヒドロキシ
化合物を加えて反応を行なう第２工程の２工程か
らなり、第１工程で着色が起り易いと共に製造工
程が複雑であり、また製造に長時間を要するとい
う欠点がある。
さらに、このようにして得られるリン酸エステ
ルはリン酸系特有の臭気がありシヤンプー、洗浄
剤等の人体に直接使用する製品には適していな
い。
リン酸エステルの脱臭方法としては、リン酸エ
ステルを薄膜液状とし水蒸気等の不活性ガスと接
触し脱臭する方法（特公昭57−35595）が報告さ
れているが、リン酸エステルと不活性ガスとの接
触方法のコントロールが難かしく、接触時間が長
いとリン酸エステルが分解し、収率が低下すると
いう欠点があつた。
本発明は上記の点に着目しなされたもので、洗
浄剤、乳化剤、繊維処理剤、帯電防止剤、潤滑油
添加剤、防錆剤等の用途に適したリン酸モノエス
テル含量が多く、しかも色相が良好で臭気の少な
いリン酸エステルの製造方法を提供することを目
的とする。
〔問題点を解決するための手段〕
本発明者らは上記の課題を解決するため鋭意研
究した結果、水蒸気を吹き込みながらリン酸エス
テル化反応を行なうことにより、反応工程が簡単
でリン酸モノエステルの生成量が増加し、かつ色
相、臭気の良好なリン酸エステルを製造する方法
を見い出し本発明に至つた。
すなわち本発明は、水の存在下に脂肪族アルコ
ール類と五酸化リンとを反応しリン酸エステルを
製造するに当り、脂肪族アルコール類に水と五酸
化リンを加え、ついで水蒸気を吹き込みながらリ
ン酸エステル化反応を行なうリン酸エステルの製
造方法である。
本発明に用いる脂肪族アルコール類としては炭
素数８〜24の飽和又は及び不飽和性の脂肪族アル
コール、及びこの脂肪族アルコールの低級アルキ
レンオキサイド付加体である。脂肪族アルコール
は、そのアルキル基部分に直鎖性アルキル基又は
及び側鎖性アルキル基を含み、炭素数８〜24の直
鎖飽和アルコール、炭素数１〜11の側鎖を有する
総炭素数８〜24の側鎖飽和アルコールまたは天然
油脂を分解して得られる脂肪酸を還元して得られ
る炭素数８〜24の還元アルコールまたはα−オレ
フインを原料としてオキソ法等により得られる側
鎖アルキル基を含む合成アルコールが挙げられ
る。例えばオクタノール、イソオクタノール、ノ
ニルアルコール、デシルアルコール、ウンデシル
アルコール、ラウリルアルコール、トリデシルア
ルコール、ペンタデシルアルコール、ヘプタデシ
ルアルコール、ノナデシルアルコール、ヤシ油還
元アルコール、牛脂還元アルコール、ミリスチル
アルコール、セタノール、オレイルアルコール、
ステアリルアルコール、ナタネ油還元アルコー
ル、魚油還元アルコール、水添魚油の還元アルコ
ール等があり、さらに合成アルコールとして商品
名オキソコール（日産化学工業(株)製）、ドバノー
ル（三菱油化(株)製）、ダイアドール（三菱化成工
業(株)製）等が挙げられる。
脂肪族アルコールの低級アルキレンオキサイド
としては上記脂肪族アルコールにエチレンオキサ
イド、プロピレンオキサイド等の低級アルキレン
オキサイドを１〜20モル付加した付加体が挙げら
れ、例えば商品名ソフタノール30（日本触媒化学
(株)製）が挙げられる。
本発明の方法により、リン酸エステルを製造す
るには、脂肪族アルコール類と水を仕込み、五酸
化リンを添加し、20〜90℃で0.5〜10時間反応を
行ないついで水蒸気を吹き込みながら90〜110℃
で10〜180分間リン酸エステル化反応を行なう。
脂肪族アルコール類と水と五酸化リンとの反応比
はモル比で1.0〜5.0：0.5〜1.5：１が好ましい。
脂肪族アルコール類の量は五酸化リン１モルに対
し1.0モル以下ではオルソリン酸の生成量が多く、
色調が悪い。5.0モル以上ではリン酸ジエステル、
トリエステルの生成量が多くなる。水の量は五酸
化リン１モルに対し0.5モル以下ではリン酸ジエ
ステルの生成量が多く、1.5モル以上ではリン酸
の反応率が低下し、またオルソリン酸の生成量が
増加する。
水蒸気の吹き込みは仕込んだ脂肪族アルコール
類１Kg当り0.04〜20m3／HR（N.T.P.換算値、以
下m3／HRはN.T.P.換算値を示す）の吹き込み速
度が好ましく、この範囲の水蒸気の吹き込み下に
リン酸エステル化反応を行なうとリン酸モノエス
テルの生成量が増加する。水蒸気の吹き込み量が
0.04m3／HR以下ではリン酸モノエステルの生成
量が従来法と同等で改良されず、また20m3／HR
以上ではリン酸エステルの加水分解が起り収率が
低下する。
水蒸気の吹き込み時間は10〜180分間が好まし
く、リン酸モノエステル含量が多くリン酸ジエス
テル含量の少ないリン酸エステルが得られる。10
分以下ではリン酸モノエステル含量が増加せず、
180分以上ではリン酸ジエステル含量は少ないが
リン酸モノエステル含量も低下する。
本発明は水蒸気を吹き込みながらリン酸エステ
ル化反応を行なうことにより、リン酸モノエステ
ル含量の多いリン酸エステルが製造できることを
見い出したものであり、次のような現象が認めら
れた。
五酸化リンを添加した後、水蒸気を吹き込み
ながらリン酸エステル化反応を行なうとリン酸
エステル含量が多く、リン酸ジエステル含量の
少ないリン酸エステルが得られる。
五酸化リンを添加した後、一定時間反応し次
に水蒸気の吹き込みを開始し反応を継続する
と、水蒸気吹き込み開始前に生成していたリン
酸ジエステル含量が低下し、リン酸モノエステ
ル含量が多くなる。
すなわち水蒸気の吹き込み開始は五酸化リンの
添加終了直後、または終了後一定時間反応した後
に行なつても良い。
水蒸気の吹き込み前に行なう反応は20〜90℃で
10時間以内が好ましく、それより反応時間が長い
とリン酸エステルの加水分解が促進され収率が低
下する。
以上のように本発明の製造方法は少ない工程で
効率良くリン酸モノエステルの含量を高めること
ができ、さらには従来品と比較して色相が良好で
臭気の少ないリン酸エステルが得られる。
本発明の製造方法により得られるリン酸エステ
ルは洗浄剤、乳化剤、繊維処理剤、帯電防止剤、
潤滑油添加剤、防錆剤等に適する。
〔実施例〕
以下実施例により本発明をさらに詳しく説明す
る。
実施例 １
水蒸気導入管を備えた1000mlの反応容器に、ラ
ウリルアルコール409ｇ（2.2モル）及び水18ｇ
（1.0モル）を仕込み、攪拌し、温度を50〜60℃に
保ちながら五酸化リン142ｇ（1.0モル）を添加
し、同温度で３時間反応を行なつた。ここに得ら
れた反応混合物はラウリルリン酸モノエステル
69.2％、ラウリルリン酸ジエステル30.5％を含有
していた。
この反応混合物を95〜100℃に昇温し、攪拌下
同温度で水蒸気導入管より反応混合物中に0.32
m3／HR（アルコール１Kg当り0.56m3／HR）の水
蒸気を60分間導入して、ラウリルリン酸モノエス
テル89％、ラウリルリン酸ジエステル8.1％のモ
ノエステル含量の高いリン酸エステルを得た。得
られたリン酸エステルは臭気が少なく、色相も良
好であつた。
又さらに前記水蒸気の導入反応を３時間まで行
ない、水蒸気導入反応中のラウリルリン酸モノエ
ステル及びラウリルリン酸ジエステルの含量を測
定し、その結果を表−１に示す。
なお、ラウリルリン酸モノエステル及びラウリ
ルリン酸ジエステルの含量の測定は以下のように
行なつた。
0.2〜0.3ｇのサンプルを65v／ｖ％エタノール
水溶液100mlに溶解し、１／10N水酸化ナトリウ
ム水溶液で滴定を行ない、得られた滴定結果より
第１中和点、第２中和点、第３中和点を求め、モ
ノエステル、ジエステルの含量を下記の式により
算出した。但し、第３中和点は前記とは別にサン
プルのエタノール水溶液を調整し、これに1N硝
酸銀溶液10mlを添加し、10分間放置した後上記と
同様に１／10N水酸化ナトリウム溶液で滴定を行
なつた。
モノエステル濃度（重量％）
＝（2b−ａ−ｃ）×Ｎ×ｆ×Ｍ×100÷（Ｓ−Ｗ）
ジエステル濃度（重量％）
＝（2a−ｂ）×Ｎ×ｆ×Ｄ×100÷（Ｓ−Ｗ）
但し、式中ａは第１中和点に要したアルカリ溶
液の滴定量（ml）、ｂは第２中和点に要したアル
カリ溶液の滴定量（ml）、ｃは第３中和点に要し
たアルカリ溶液の滴定量（ml）、Ｎはアルカリ溶
液の規定度、ｆはアルカリ溶液の力価、Ｍはモノ
エステルの分子量、Ｄはジエステルの分子量、Ｓ
はサンプル量（mg）、Ｗはサンプル中の水分（mg）
をそれぞれ示す。
比較例 １
実施例１に用いた反応容器にラウリルアルコー
ル409ｇ（2.2モル）及び水18ｇ（1.0モル）を仕
込み、混合した後実施例１と同様に50〜60℃で五
酸化リン142ｇ（1.0モル）を添加し同温度で３時
間反応を行なつた。
次にこの反応混合物を95〜100℃に昇温し同温
度で３時間反応を行ないリン酸エステルを得た。
得られたリン酸エステルは暗褐色で色相が悪く、
高級アルコール様の特異臭があつた。
また95〜100℃加熱反応時のモノエステル、ジ
エステルの含量を一定時間ごとに測定した所、加
熱反応前に比べモノエステルの増加は少かつた。
その結果を表−１に示す。
比較例 ２
実施例１に用いた反応容器にラウリルアルコー
ル409ｇ（2.2モル）仕込み、液温を50〜60℃に保
ちながら五酸化リン142ｇ（1.0モル）を添加し、
同温度で３時間反応を行なつた。この反応混合物
中のラウリルリン酸モノエステル含量は17.9％、
ラウリルリン酸ジエステル含量は66.6％であつ
た。
次にこの反応混合物を95〜100℃に昇温し、同
温度で反応混合物液中に0.32m3／HR（アルコール
１Kg当り0.58m3／Hr）の水蒸気を３時間導入し
た。
水蒸気導入反応中のモノエステル、ジエステル
の含量を一定時間ごとに測定しその結果を表−１
に示す。
[Industrial Field of Application] The present invention relates to a method for producing a phosphoric acid ester with a high content of phosphoric acid monoester. More specifically, the present invention relates to a method for producing a phosphoric acid ester that can easily produce a phosphoric acid ester with a high content of phosphoric acid monoester and that has good hue, odor, etc. of the obtained phosphoric acid ester. [Prior art] Phosphate esters obtained by phosphorylating organic hydroxy compounds can be used as detergents, emulsifiers, fiber treatment agents,
Widely used in antistatic agents, lubricating oil additives, rust preventives, pharmaceuticals, etc. Usually, when an organic hydroxy compound is subjected to a phosphoric acid esterification reaction using phosphorus pentoxide as a phosphorylating agent, a substantially equimolar mixture of a phosphoric monoester and a phosphoric diester is obtained. Phosphoric acid monoesters and phosphoric acid diesters are significantly different in performance; phosphoric acid monoesters have good water solubility, foaming power, and detergency, while phosphoric acid diesters are inferior in these abilities. That is, phosphoric acid esters used in detergents, shampoos, etc. are desired to have a high content of phosphoric acid monoester. Conventionally, various methods for producing phosphoric acid esters with a high content of phosphoric acid monoester have been proposed, but as a method for carrying out the phosphoric acid esterification reaction in the presence of water, (1) adding water to an organic hydroxy compound has been proposed. (2) A method in which an organic hydroxy compound is reacted with water and a phosphorylating agent, and then an organic hydroxy compound is added to the product ( JP-A-56-86191), etc. [Problems to be solved by the invention] However, method (1) has drawbacks such as poor reaction rate of phosphoric anhydride and a large amount of orthophosphoric acid produced and mixed into the product. It consists of two steps: the first step in which the phosphoric acid esterification reaction is carried out in a state where the phosphoric acid content is in excess, and the second step in which the reaction is carried out by adding a stoichiometric amount of an organic hydroxy compound to this product. The drawbacks are that coloring is likely to occur, the manufacturing process is complicated, and manufacturing takes a long time. Furthermore, the phosphoric acid ester thus obtained has an odor characteristic of phosphoric acids, and is not suitable for products to be used directly on the human body, such as shampoos and detergents. As a method for deodorizing phosphoric acid esters, a method has been reported in which phosphoric acid esters are made into a thin liquid film and deodorized by contacting with an inert gas such as water vapor (Japanese Patent Publication No. 57-35595). It is difficult to control the contact method, and if the contact time is long, the phosphoric acid ester decomposes and the yield decreases. The present invention was developed with attention to the above points, and has a high phosphoric acid monoester content suitable for uses such as detergents, emulsifiers, fiber treatment agents, antistatic agents, lubricating oil additives, and rust preventive agents. An object of the present invention is to provide a method for producing a phosphoric acid ester having a good hue and low odor. [Means for Solving the Problems] As a result of intensive research in order to solve the above-mentioned problems, the present inventors found that by carrying out the phosphoric acid esterification reaction while blowing water vapor, the reaction process is simple and phosphoric acid monoester can be produced. The present inventors have discovered a method for producing a phosphoric acid ester that increases the amount of phosphoric acid produced and has good color and odor, leading to the present invention. That is, in the present invention, when producing a phosphoric acid ester by reacting aliphatic alcohols and phosphorus pentoxide in the presence of water, water and phosphorus pentoxide are added to the aliphatic alcohol, and then phosphorus is added to the aliphatic alcohol while blowing in steam. This is a method for producing a phosphoric acid ester by carrying out an acid esterification reaction. The aliphatic alcohols used in the present invention include saturated or unsaturated aliphatic alcohols having 8 to 24 carbon atoms, and lower alkylene oxide adducts of these aliphatic alcohols. Aliphatic alcohols include straight chain alkyl groups or side chain alkyl groups in their alkyl group portions, straight chain saturated alcohols having 8 to 24 carbon atoms, and straight chain saturated alcohols having side chains having 1 to 11 carbon atoms and a total of 8 carbon atoms. Contains side chain saturated alcohols with ~24 carbon atoms, reduced alcohols with 8 to 24 carbon atoms obtained by reducing fatty acids obtained by decomposing natural oils, or side chain alkyl groups obtained by the oxo method using α-olefin as raw materials. Examples include synthetic alcohols. For example, octanol, isooctanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, pentadecyl alcohol, heptadecyl alcohol, nonadecyl alcohol, coconut oil reduced alcohol, tallow reduced alcohol, myristyl alcohol, cetanol, oleyl alcohol,
There are stearyl alcohol, rapeseed oil reduced alcohol, fish oil reduced alcohol, and hydrogenated fish oil reduced alcohol, and synthetic alcohols such as Oxocol (manufactured by Nissan Chemical Industries, Ltd.), Dovanol (manufactured by Mitsubishi Yuka Co., Ltd.), Examples include Diador (manufactured by Mitsubishi Chemical Industries, Ltd.). Examples of lower alkylene oxides of aliphatic alcohols include adducts in which 1 to 20 moles of lower alkylene oxides such as ethylene oxide and propylene oxide are added to the above aliphatic alcohols.
Co., Ltd.). In order to produce a phosphoric acid ester according to the method of the present invention, aliphatic alcohols and water are prepared, phosphorus pentoxide is added, and the reaction is carried out at 20 to 90°C for 0.5 to 10 hours. 110℃
Perform the phosphoric acid esterification reaction for 10 to 180 minutes.
The reaction ratio of aliphatic alcohol, water and phosphorus pentoxide is preferably 1.0-5.0:0.5-1.5:1 in molar ratio.
If the amount of aliphatic alcohol is less than 1.0 mol per 1 mol of phosphorus pentoxide, a large amount of orthophosphoric acid will be produced.
The color tone is bad. If 5.0 moles or more, phosphoric acid diester,
The amount of triester produced increases. If the amount of water is less than 0.5 mole per mole of phosphorus pentoxide, a large amount of phosphoric acid diester will be produced, and if it is more than 1.5 mole, the reaction rate of phosphoric acid will decrease and the amount of orthophosphoric acid produced will increase. It is preferable that the steam be blown at a speed of 0.04 to 20 m 3 /HR (NTP equivalent value, hereinafter m 3 /HR shows the NTP equivalent value) per 1 kg of the aliphatic alcohol charged, and the phosphorus should be blown in this range. When the acid esterification reaction is performed, the amount of phosphoric acid monoester produced increases. The amount of water vapor blown into
Below 0.04 m 3 /HR, the amount of phosphoric acid monoester produced is the same as that of the conventional method and there is no improvement;
Above this amount, hydrolysis of the phosphoric acid ester occurs and the yield decreases. The steam blowing time is preferably 10 to 180 minutes, and a phosphoric ester containing a large amount of phosphoric acid monoester and a small amount of phosphoric acid diester can be obtained. Ten
Below minutes, the phosphoric acid monoester content does not increase,
At 180 minutes or more, the phosphoric acid diester content is small, but the phosphoric acid monoester content also decreases. In the present invention, it has been discovered that a phosphoric acid ester with a high content of phosphoric acid monoester can be produced by carrying out a phosphoric acid esterification reaction while blowing in steam, and the following phenomenon was observed. After adding phosphorus pentoxide, a phosphoric acid esterification reaction is carried out while blowing in water vapor to obtain a phosphoric ester containing a large amount of phosphoric ester and a small amount of diester phosphoric acid. After adding phosphorus pentoxide, if the reaction is continued for a certain period of time, then steam injection is started and the reaction is continued, the phosphoric acid diester content that was generated before the steam injection started decreases, and the phosphoric acid monoester content increases. . That is, the introduction of water vapor may be started immediately after the addition of phosphorus pentoxide is completed, or after the reaction has continued for a certain period of time after the addition of phosphorus pentoxide. The reaction is carried out at 20 to 90℃ before steam injection.
The reaction time is preferably within 10 hours; if the reaction time is longer than that, hydrolysis of the phosphate ester will be accelerated and the yield will be reduced. As described above, the production method of the present invention can efficiently increase the content of phosphoric acid monoester with a small number of steps, and can also obtain a phosphoric ester with a better hue and less odor than conventional products. The phosphoric acid ester obtained by the production method of the present invention can be used as a detergent, an emulsifier, a fiber treatment agent, an antistatic agent,
Suitable for lubricating oil additives, rust preventives, etc. [Example] The present invention will be explained in more detail with reference to Examples below. Example 1 409 g (2.2 mol) of lauryl alcohol and 18 g of water were placed in a 1000 ml reaction vessel equipped with a steam introduction tube.
(1.0 mol) was charged, stirred, and while maintaining the temperature at 50 to 60°C, 142 g (1.0 mol) of phosphorus pentoxide was added, and the reaction was carried out at the same temperature for 3 hours. The reaction mixture obtained here is lauryl phosphate monoester
It contained 69.2% and 30.5% lauryl phosphate diester. The temperature of this reaction mixture was raised to 95-100°C, and while stirring, 0.32%
Steam of m 3 /HR (0.56 m 3 /HR per 1 kg of alcohol) was introduced for 60 minutes to obtain a phosphoric acid ester with a high monoester content of 89% lauryl phosphate monoester and 8.1% lauryl phosphoric diester. The obtained phosphoric acid ester had little odor and good color. Further, the steam introduction reaction was continued for up to 3 hours, and the contents of lauryl phosphate monoester and lauryl phosphate diester in the steam introduction reaction were measured, and the results are shown in Table 1. The content of lauryl phosphate monoester and lauryl phosphate diester was measured as follows. Dissolve 0.2~0.3g of the sample in 100ml of 65v/v% ethanol aqueous solution, titrate with 1/10N sodium hydroxide aqueous solution, and determine the first neutralization point, second neutralization point, and third neutralization point from the titration results obtained. The neutralization point was determined, and the content of monoester and diester was calculated using the following formula. However, for the third neutralization point, prepare a sample ethanol aqueous solution separately from the above, add 10 ml of 1N silver nitrate solution, leave it for 10 minutes, and then titrate with 1/10N sodium hydroxide solution in the same way as above. Summer. Monoester concentration (wt%) = (2b-a-c) x N x f x M x 100÷ (S-W) Diester concentration (wt%) = (2a-b) x N x f x D x 100÷ (S-W) However, in the formula, a is the titration amount (ml) of the alkaline solution required to reach the first neutralization point, b is the titration amount (ml) of the alkaline solution required to reach the second neutralization point, and c is the titration amount (ml) of the alkaline solution required to reach the second neutralization point. 3 Titration amount (ml) of alkaline solution required for neutralization point, N is normality of alkaline solution, f is titer of alkaline solution, M is molecular weight of monoester, D is molecular weight of diester, S
is the sample amount (mg), W is the water content in the sample (mg)
are shown respectively. Comparative Example 1 409 g (2.2 mol) of lauryl alcohol and 18 g (1.0 mol) of water were charged into the reaction vessel used in Example 1, and after mixing, 142 g (1.0 mol) of phosphorus pentoxide was added at 50 to 60°C in the same manner as in Example 1. ) was added thereto and the reaction was carried out at the same temperature for 3 hours. Next, this reaction mixture was heated to 95 to 100°C, and the reaction was carried out at the same temperature for 3 hours to obtain a phosphoric acid ester.
The obtained phosphoric acid ester was dark brown and had a poor hue.
It had a distinctive odor similar to high alcohol. Furthermore, when the contents of monoester and diester during the heating reaction at 95 to 100°C were measured at regular intervals, the increase in monoester was smaller than before the heating reaction.
The results are shown in Table-1. Comparative Example 2 409 g (2.2 mol) of lauryl alcohol was charged into the reaction vessel used in Example 1, and 142 g (1.0 mol) of phosphorus pentoxide was added while maintaining the liquid temperature at 50 to 60°C.
The reaction was carried out at the same temperature for 3 hours. The lauryl phosphate monoester content in this reaction mixture was 17.9%;
The lauryl phosphate diester content was 66.6%. Next, this reaction mixture was heated to 95 to 100°C, and at the same temperature, 0.32 m 3 /HR (0.58 m 3 /Hr per 1 kg of alcohol) of water vapor was introduced into the reaction mixture for 3 hours. The content of monoester and diester during the steam introduction reaction was measured at regular intervals and the results are shown in Table 1.
Shown below.
【表】
＊ 実施例１及び比較例２では水蒸気の導入
反応時間 比較例１では加熱反応時
間を各々示す。
実施例 ２
実施例１に用いた反応容器にラウリルアルコー
ル409ｇ（2.2モル）及び水18ｇ（1.0モル）を仕
込み、混合した後実施例１と同様に50〜60℃で五
酸化リン142ｇ（1.0モル）を添加し同温度で２時
間反応を行なつた。
次にこの反応混合物を95〜100℃に昇温し、同
温度で反応混合物１Kg当り水蒸気を0.02〜25m3／
HRの速度で１時間導入しリン酸エステルを得
た。
得られたリン酸エステル中のラウリルリン酸モ
ノエステル及びラウリルリン酸ジエステルの含量
を測定しその結果を表−２に示す。[Table] * In Example 1 and Comparative Example 2, the water vapor introduction reaction time. In Comparative Example 1, the heating reaction time
The intervals are shown respectively.
Example 2 In the reaction vessel used in Example 1, 409 g (2.2 mol) of lauryl alcohol and 18 g (1.0 mol) of water were charged and mixed, and then 142 g (1.0 mol) of phosphorus pentoxide was added at 50 to 60°C in the same manner as in Example 1. ) was added thereto and the reaction was carried out at the same temperature for 2 hours. Next, the temperature of this reaction mixture is raised to 95-100°C, and at the same temperature, 0.02-25 m 3 / of water vapor is added per 1 kg of reaction mixture.
The mixture was introduced at a HR rate for 1 hour to obtain a phosphoric acid ester. The contents of lauryl phosphate monoester and lauryl phosphate diester in the obtained phosphoric ester were measured, and the results are shown in Table 2.
以上説明したように本発明は脂肪族アルコール
類と水と五酸化リンを加え、ついで水蒸気を吹き
込みながらエステル化反応を行ないリン酸エステ
ルを製造する方法であり、本発明の方法によれば
As explained above, the present invention is a method for producing a phosphoric acid ester by adding aliphatic alcohols, water, and phosphorus pentoxide, and then carrying out an esterification reaction while blowing in steam.
【表】
モノエステル含量の高いリン酸エステルを容易
に製造することができ、得られたリン酸エステル
は水溶性、起泡力、洗浄力に優れ、かつ臭気が少
なく、色相が良好でシヤンプー、洗浄剤等の原材
料に適し、従来のリン酸エステルと比較し、少な
い添加量で同等の界面活性能を発揮し経済性に優
れ、又シヤンプー、洗浄剤等に添加して得られる
製品の人体に対する刺激が少なくあるいは不快感
を与えない等の効果を有する。[Table] A phosphoric ester with a high monoester content can be easily produced, and the obtained phosphoric ester has excellent water solubility, foaming power, and detergency, has little odor, has a good color, and is a shampoo, Suitable as a raw material for detergents, etc. Compared to conventional phosphoric acid esters, it exhibits the same surfactant ability with a smaller amount of addition, and is highly economical.It is also effective against the human body when added to shampoos, detergents, etc. It has the effect of being less irritating or causing no discomfort.
Claims (1)
ンとを反応し、リン酸エステルを製造するに当
り、脂肪族アルコール類に水と五酸化リンを加
え、ついで水蒸気を吹き込みながらリン酸エステ
ル化反応を行なうことを特徴とするリン酸エステ
ルの製造方法。 ２ 脂肪族アルコール類と水と五酸化リンとの反
応比がモル比で各々1.0〜5.0：0.5〜1.5：１であ
る特許請求の範囲第１項記載のリン酸エステルの
製造方法。 ３ 水蒸気の吹き込みを、脂肪族アルコール類１
Kg当り0.04〜20m3／HR（N.T.P.換算値）の吹き
込み速度で10〜180分間行なう特許請求の範囲第
１項又は第２項記載のリン酸エステルの製造方
法。[Claims] 1. In producing a phosphoric acid ester by reacting aliphatic alcohols with phosphorus pentoxide in the presence of water, water and phosphorus pentoxide are added to the aliphatic alcohol, and then steam is added. A method for producing a phosphoric acid ester, characterized by carrying out a phosphoric acid esterification reaction while blowing. 2. The method for producing a phosphoric acid ester according to claim 1, wherein the reaction ratio of aliphatic alcohol, water, and phosphorus pentoxide is 1.0 to 5.0:0.5 to 1.5:1 in molar ratio, respectively. 3 Blow steam into the aliphatic alcohol 1
The method for producing a phosphoric acid ester according to claim 1 or 2, wherein the process is carried out for 10 to 180 minutes at a blowing rate of 0.04 to 20 m 3 /HR (NTP equivalent value) per kg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17393485A JPS6233190A (en) | 1985-08-07 | 1985-08-07 | Production of phosphoric acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17393485A JPS6233190A (en) | 1985-08-07 | 1985-08-07 | Production of phosphoric acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6233190A JPS6233190A (en) | 1987-02-13 |
| JPH0566958B2 true JPH0566958B2 (en) | 1993-09-22 |
Family
ID=15969776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17393485A Granted JPS6233190A (en) | 1985-08-07 | 1985-08-07 | Production of phosphoric acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6233190A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3115489B2 (en) * | 1994-09-20 | 2000-12-04 | 花王株式会社 | Method for producing phosphate monoester |
| KR100261858B1 (en) * | 1994-12-09 | 2000-07-15 | 고토다쿠야 | Process for the preparation of phosphoric monoester |
| CN109879906B (en) * | 2019-04-02 | 2021-05-07 | 上海多纶化工有限公司 | Process for the preparation of phosphoric esters |
-
1985
- 1985-08-07 JP JP17393485A patent/JPS6233190A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6233190A (en) | 1987-02-13 |
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