JP6077400B2 - Process for producing polyoxyalkylene alkyl ether acetate - Google Patents
Process for producing polyoxyalkylene alkyl ether acetate Download PDFInfo
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- JP6077400B2 JP6077400B2 JP2013134581A JP2013134581A JP6077400B2 JP 6077400 B2 JP6077400 B2 JP 6077400B2 JP 2013134581 A JP2013134581 A JP 2013134581A JP 2013134581 A JP2013134581 A JP 2013134581A JP 6077400 B2 JP6077400 B2 JP 6077400B2
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- alkyl ether
- polyoxyalkylene alkyl
- ether acetate
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- -1 alkyl ether acetate Chemical class 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 239000003054 catalyst Substances 0.000 claims description 47
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 229910000510 noble metal Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 238000003860 storage Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 150000005215 alkyl ethers Chemical class 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims 3
- 125000000217 alkyl group Chemical group 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 230000006866 deterioration Effects 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000001953 sensory effect Effects 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000003761 preservation solution Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、ポリオキシアルキレンアルキルエーテル酢酸塩の製造方法に関し、特に新規な保存方法を含むポリオキシアルキレンアルキルエーテル酢酸塩の製造方法に関する。 The present invention relates to a method for producing a polyoxyalkylene alkyl ether acetate, and more particularly to a method for producing a polyoxyalkylene alkyl ether acetate including a novel storage method.
ポリオキシアルキレンアルキルエーテル酢酸塩は、ポリオキシアルキレンアルキルエーテルの末端をカルボン酸で置換した化合物であり、化粧品、乳化剤、可溶化剤、分散剤、ゲル化剤、洗浄基剤等に使用することができる界面活性剤として知られている。 Polyoxyalkylene alkyl ether acetate is a compound in which the terminal of polyoxyalkylene alkyl ether is substituted with carboxylic acid, and can be used in cosmetics, emulsifiers, solubilizers, dispersants, gelling agents, cleaning bases, etc. It is known as a surfactant that can be used.
ポリオキシアルキレンアルキルエーテル酢酸塩の製造方法は種々知られているが、その一つに、貴金属触媒の存在下でポリオキシアルキレンアルキルエーテルを酸素酸化させる方法がある（特許文献１〜３）。また、特許文献４には、ポリアルコキシアルコールまたは脂肪アルコールアルコキシレートを酸化してエーテル酢酸を製造するにあたり、ポリアルコキシアルコールまたは脂肪アルコールアルコキシレートに反応生成物と同じエーテル酢酸を予め加えてから反応を行う方法が記載されている。 Various methods for producing polyoxyalkylene alkyl ether acetates are known, and one of them is a method in which polyoxyalkylene alkyl ether is oxidized with oxygen in the presence of a noble metal catalyst (Patent Documents 1 to 3). Further, in Patent Document 4, in producing ether acetic acid by oxidizing polyalkoxy alcohol or fatty alcohol alkoxylate, the reaction is performed after adding the same ether acetic acid as the reaction product to polyalkoxy alcohol or fatty alcohol alkoxylate in advance. The method of doing is described.
一般に、貴金属触媒の存在下でポリオキシアルキレンアルキルエーテルを酸素酸化させる方法では、ある程度の反応率（例えば６０％程度）を得るために比較的長時間を要する。従って工業的に製造を行う場合、反応時間を短縮することが望まれる。特許文献４の製法は、反応時間を短縮し得る方法であるとされているが、におい等、品質の良いポリオキシアルキレンアルキルエーテル酢酸を安定的に製造するための具体的な条件等については十分に言及されていない。 In general, in the method in which polyoxyalkylene alkyl ether is oxidized with oxygen in the presence of a noble metal catalyst, it takes a relatively long time to obtain a certain degree of reaction rate (for example, about 60%). Therefore, when manufacturing industrially, it is desired to shorten the reaction time. The production method of Patent Document 4 is said to be a method that can shorten the reaction time, but it is sufficient for specific conditions for stably producing high-quality polyoxyalkylene alkyl ether acetic acid such as odor. Not mentioned.
特許文献４のような知見に関連する、回分型反応器における反応時間短縮のための工業的に有用な手段としては、反応終了後の反応液をある程度反応槽に残留させて保存し、次の反応開始時にその状態から反応を開始して、保存された残留物を予め添加される反応生成物として用いることが挙げられる。しかし、反応槽に残留させたまま保存すると数日でにおいが悪化し、これを用いて製造した製品のにおいも悪化してしまうという問題がある。またこのような場合以外にも、製造現場の都合によって反応工程の途中で待機状態となる状況があり、そのような場合にも製品のにおいが悪化する問題がある。本発明は、このような問題を解決し、品質の良いポリオキシアルキレンアルキルエーテル酢酸塩を安定的に製造できる方法を提供することを課題としている。 As an industrially useful means for shortening the reaction time in a batch reactor related to the knowledge as in Patent Document 4, the reaction solution after completion of the reaction is left in the reaction tank to some extent and stored. The reaction is started from that state at the start of the reaction, and the stored residue is used as a reaction product to be added in advance. However, if it is stored in the reaction vessel, the odor will deteriorate in a few days, and the odor of a product manufactured using this will also deteriorate. In addition to such a case, there is a situation where a standby state occurs during the reaction process due to the convenience of the manufacturing site, and in such a case, there is a problem that the odor of the product deteriorates. An object of the present invention is to solve such problems and to provide a method capable of stably producing a high-quality polyoxyalkylene alkyl ether acetate.
本発明は、貴金属触媒（Ｂ）を含むポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の水溶液の保存方法であって、水溶液中の（Ａ）の濃度を５質量％以上、１５質量％以下とし、温度を２０℃以上、４０℃未満として保存する、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の水溶液の保存方法を提供する。この保存方法はポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の製造に関連して好ましく用いられ、従って本発明はまた、下記工程１〜５を繰り返す、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の製造方法をも提供する。 The present invention is a method for preserving an aqueous solution of a polyoxyalkylene alkyl ether acetate (A) containing a noble metal catalyst (B), wherein the concentration of (A) in the aqueous solution is 5 mass% or more and 15 mass% or less, Provided is a method for storing an aqueous solution of polyoxyalkylene alkyl ether acetate (A), which is stored at a temperature of 20 ° C. or higher and lower than 40 ° C. This storage method is preferably used in connection with the production of polyoxyalkylene alkyl ether acetate (A), and therefore the present invention also repeats steps 1-5 below to produce polyoxyalkylene alkyl ether acetate (A). A method is also provided.
工程１：反応容器内の水性媒体中で、貴金属触媒（Ｂ）の存在下に、ポリオキシアルキレンアルキルエーテルを酸素と接触させて酸化し、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）を含有する反応液を得る工程
工程２：工程１で得られた反応液の３０質量％以上、９０質量％以下を反応容器から抜き出す工程
工程３：工程２の後に、反応容器内に残留する反応液に水を加えてポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が５質量％以上、１５質量％以下の水溶液に調整する工程
工程４：前記水溶液を２０℃以上、４０℃未満の温度で保存する工程
工程５：工程２〜４のいずれかの後に、ポリオキシアルキレンアルキルエーテルを添加する工程
Step 1: A reaction containing polyoxyalkylene alkyl ether acetate (A) in an aqueous medium in a reaction vessel in the presence of a noble metal catalyst (B) in contact with oxygen to oxidize the polyoxyalkylene alkyl ether acetate (A) Step 2: Obtain 30% by mass or more and 90% by mass or less of the reaction solution obtained in Step 1 Step 3: After Step 2, water is added to the reaction solution remaining in the reaction vessel. In addition, a step of adjusting the concentration of the polyoxyalkylene alkyl ether acetate (A) to an aqueous solution having a concentration of 5% by mass or more and 15% by mass or less: a step of storing the aqueous solution at a temperature of 20 ° C. or more and less than 40 ° C. 5: A step of adding polyoxyalkylene alkyl ether after any of steps 2 to 4
本発明によれば、反応槽に残留したまま保存され或いは待機状態とされるポリオキシアルキレンアルキルエーテル酢酸塩のにおいの悪化を防止できる保存方法、これを用いてにおいの少ないポリオキシアルキレンアルキルエーテル酢酸塩を製造できる方法が提供される。 According to the present invention, a storage method capable of preventing deterioration of the odor of polyoxyalkylene alkyl ether acetate which is stored in a reaction tank or is kept in a standby state, and polyoxyalkylene alkyl ether acetic acid having less odor using the same. A method is provided by which the salt can be produced.
本発明において、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）は分子内にエーテル結合とカルボン酸塩構造をもつ化合物であって、下記一般式（１）で表される化合物が好ましい。
ＲＯ−（ＡＯ）n−ＣＨ2−ＣＯＯ−Ｍ （１）
〔式中、Ｒは炭素数８以上、２４以下の炭化水素基、ＡＯは炭素数２以上、４以下の直鎖または分岐のアルキレンオキシ基、ｎはＡＯの平均付加モル数であり、０．１以上、１００以下の数、Ｍはアルカリ金属もしくはアルカリ土類金属である。アルカリ金属としてはナトリウム、カリウムから選ばれる１種以上が挙げられ、アルカリ土類金属としてはマグネシウム、カルシウムから選ばれる１種以上が挙げられる。〕
In the present invention, the polyoxyalkylene alkyl ether acetate (A) is a compound having an ether bond and a carboxylate structure in the molecule and is preferably a compound represented by the following general formula (1).
RO- (AO) n -CH 2 -COO -M (1)
[Wherein, R is a hydrocarbon group having 8 to 24 carbon atoms, AO is a linear or branched alkyleneoxy group having 2 to 4 carbon atoms, n is the average number of added moles of AO; A number of 1 or more and 100 or less, and M is an alkali metal or an alkaline earth metal. Examples of the alkali metal include one or more selected from sodium and potassium, and examples of the alkaline earth metal include one or more selected from magnesium and calcium. ]
式中の構造は、用途等に応じて適宜決定できるが洗浄基剤としての性能の観点からは、Ｒの炭素数は１０以上が好ましく、１２以上がより好ましい。また、同様の観点からＲの炭素数は１８以下が好ましく１４以下がより好ましい。また、Ｒの炭化水素基は、飽和でも不飽和でもよく、直鎖でも分岐鎖でもよく、１級でも、２級でもよい。 The structure in the formula can be appropriately determined depending on the application and the like, but from the viewpoint of performance as a cleaning base, the carbon number of R is preferably 10 or more, and more preferably 12 or more. From the same viewpoint, the carbon number of R is preferably 18 or less, and more preferably 14 or less. The hydrocarbon group for R may be saturated or unsaturated, may be linear or branched, and may be primary or secondary.
原料としての汎用性や経済性の観点からは、ＡＯは炭素数２のエチレンオキシ基が好ましく、全ＡＯのうち８０モル％以上がエチレンオキシ基であることが好ましい。反応液中における流動性の観点からは、ｎは１以上が好ましく、２以上がより好ましい。また、同様の観点からｎは１０以下が好ましく、７以下がより好ましい。尚、勿論一般式（１）で表される複数の構造の原料を混合した状態で反応することもできる。 From the viewpoint of versatility as a raw material and economy, AO is preferably an ethyleneoxy group having 2 carbon atoms, and 80 mol% or more of all AO is preferably an ethyleneoxy group. From the viewpoint of fluidity in the reaction solution, n is preferably 1 or more, and more preferably 2 or more. From the same viewpoint, n is preferably 10 or less, more preferably 7 or less. Needless to say, the reaction can be performed in a mixed state of raw materials having a plurality of structures represented by the general formula (1).
ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）は対応するポリオキシアルキレンアルキルエーテル、即ち下記一般式（２）で表される化合物を貴金属触媒（Ｂ）の存在下、酸素によって酸化することで得られる。
ＲＯ−（ＡＯ）n−ＣＨ2−ＣＨ2−ＯＨ （２）
〔式中、Ｒ及びＡＯは一般式（１）と同様の意味を表す。〕
The polyoxyalkylene alkyl ether acetate (A) is obtained by oxidizing a corresponding polyoxyalkylene alkyl ether, that is, a compound represented by the following general formula (2) with oxygen in the presence of a noble metal catalyst (B).
RO- (AO) n -CH 2 -CH 2 -OH (2)
[Wherein, R and AO represent the same meaning as in general formula (1). ]
本発明に用いられる貴金属触媒（Ｂ）は上記酸化反応を効率的に進行させるものであり、白金族元素から選ばれる１種以上の元素を含有することが好ましい。具体的には、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム及び白金から選ばれる１種以上の元素を含有することが好ましく、パラジウム及び白金から選ばれる１種以上の元素を含有することがより好ましい。 The noble metal catalyst (B) used in the present invention allows the above oxidation reaction to proceed efficiently, and preferably contains one or more elements selected from platinum group elements. Specifically, it preferably contains one or more elements selected from ruthenium, rhodium, palladium, osmium, iridium and platinum, and more preferably contains one or more elements selected from palladium and platinum.
また、貴金属触媒（Ｂ）が、白金族元素から選ばれる１種以上の元素（以下、触媒第１成分という）を含有する場合、更に、触媒成分として、スズ、ビスマス、セレン、テルル及びアンチモンから選ばれる１種以上の元素（以下、「触媒第２成分」という）を含有することが好ましい。 Further, when the noble metal catalyst (B) contains one or more elements selected from platinum group elements (hereinafter referred to as catalyst first component), the catalyst component further includes tin, bismuth, selenium, tellurium and antimony. It is preferable to contain one or more elements selected (hereinafter referred to as “catalyst second component”).
更に、貴金属触媒（Ｂ）が、触媒第１成分及び触媒第２成分を含有する場合、更に、触媒成分として、希土類元素から選ばれる１種以上の元素（以下、「触媒第３成分」という）を含有することができる。 Further, when the noble metal catalyst (B) contains the first catalyst component and the second catalyst component, the catalyst component further includes one or more elements selected from rare earth elements (hereinafter referred to as “catalyst third component”). Can be contained.
貴金属触媒（Ｂ）は、担体に担持させた担持触媒として用いるのが好ましい。担体は無機担体が好ましく、例えば、活性炭、アルミナ、シリカゲル、活性白土、珪藻土等が挙げられる。なかでも共存するアルカリ物質に対する耐久性の観点で活性炭が好ましい。触媒第１成分の担持量は、反応活性の観点から、担持触媒全体の０．１質量％以上が好ましく、１質量％以上がより好ましく、２質量％以上が更に好ましい。また、触媒第１成分の担持量は、経済性の観点から２０質量％以下が好ましく、１５質量％以下がより好ましく、１３質量％以下が更に好ましい。 The noble metal catalyst (B) is preferably used as a supported catalyst supported on a carrier. The carrier is preferably an inorganic carrier, and examples thereof include activated carbon, alumina, silica gel, activated clay, and diatomaceous earth. Among these, activated carbon is preferable from the viewpoint of durability against coexisting alkaline substances. From the viewpoint of reaction activity, the supported amount of the first catalyst component is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more of the entire supported catalyst. The amount of the first catalyst component supported is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 13% by mass or less from the viewpoint of economy.
本発明に用いられる貴金属触媒（Ｂ）は、例えば特開昭６２−２６９７４６号公報等に記載の、公知の方法で製造することができる。例えば、触媒第１成分の元素を含む化合物（塩化パラジウム、塩化白金酸等）の水溶液、触媒第２成分の元素を含む化合物（塩化ビスマス、五塩化アンチモン等）の水溶液、および必要に応じて触媒第３成分の元素を含む化合物（塩化セリウム、塩化ランタン等）の水溶液を、水中で活性炭等の担体に吸着させた後、触媒成分の還元処理を行う方法で製造できる。 The noble metal catalyst (B) used in the present invention can be produced by a known method described in, for example, JP-A-62-269746. For example, an aqueous solution of a compound (palladium chloride, chloroplatinic acid, etc.) containing an element of the first catalyst component, an aqueous solution of a compound (bismuth chloride, antimony pentachloride, etc.) containing an element of the second catalyst component, and a catalyst if necessary It can be produced by a method in which an aqueous solution of a compound containing a third component element (cerium chloride, lanthanum chloride, etc.) is adsorbed on a carrier such as activated carbon in water and then the catalyst component is reduced.
酸化反応に用いる酸素としては、酸素ガス、酸素を窒素で希釈した酸素含有ガス、空気などの種々の酸素含有気体を用いることができるが、反応速度の観点から酸素濃度８０％以上、１００％以下のものが好ましい。 As oxygen used in the oxidation reaction, various oxygen-containing gases such as oxygen gas, oxygen-containing gas obtained by diluting oxygen with nitrogen, and air can be used. From the viewpoint of reaction rate, the oxygen concentration is 80% or more and 100% or less. Are preferred.
本発明の保存方法によれば、ポリオキシアルキレンアルキルエーテルを貴金属触媒（Ｂ）の存在下、酸素によって酸化することで得られる、貴金属触媒（Ｂ）を含むポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の水溶液は、水溶液中の（Ａ）の濃度が５質量％以上、１５質量％以下であり、温度が２０℃以上、４０℃未満となるように調整されて保存される。 According to the preservation method of the present invention, a polyoxyalkylene alkyl ether acetate (A) containing a noble metal catalyst (B) obtained by oxidizing a polyoxyalkylene alkyl ether with oxygen in the presence of a noble metal catalyst (B). The aqueous solution is adjusted and stored so that the concentration of (A) in the aqueous solution is 5% by mass or more and 15% by mass or less, and the temperature is 20 ° C. or more and less than 40 ° C.
上に述べたように、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）を貴金属触媒（Ｂ）と接触させたまま保存すると、製品のにおいが悪化する問題がある。本発明者らの知見によれば、においの悪化を防ぐためには、保存中の（Ａ）と（Ｂ）との接触頻度を少なくする必要があり、そのためには水を添加して（Ａ）の濃度を低くすることが有効である。においの悪化を防ぐ観点から、（Ａ）の濃度は１５質量％以下であり、１３質量％以下にすることが好ましい。一方経済的な観点からは、（Ａ）の濃度は５質量％以上であり、７質量％以上にすることが好ましい。また、においの悪化防止と経済的な観点から（Ａ）の濃度は５〜１５質量％であり、７〜１３質量％が好ましい。 As described above, when the polyoxyalkylene alkyl ether acetate (A) is stored in contact with the noble metal catalyst (B), there is a problem that the odor of the product is deteriorated. According to the knowledge of the present inventors, in order to prevent the deterioration of odor, it is necessary to reduce the contact frequency between (A) and (B) during storage, and for that purpose, water is added (A). It is effective to reduce the concentration of. From the viewpoint of preventing odor deterioration, the concentration of (A) is 15% by mass or less, and preferably 13% by mass or less. On the other hand, from the economical viewpoint, the concentration of (A) is 5% by mass or more, and preferably 7% by mass or more. Moreover, the density | concentration of (A) is 5-15 mass% from the prevention of an odor deterioration and an economical viewpoint, and 7-13 mass% is preferable.
保存開始時における（Ａ）の濃度範囲が上記濃度範囲よりも高い場合には、保存開始前に水を加えて希釈し、上記濃度範囲となるように調整する。なお、保存開始時に水を添加した場合は、その水を反応時に添加する水としてそのまま使用できる。 When the concentration range of (A) at the start of storage is higher than the above concentration range, water is added to dilute before the start of storage to adjust the concentration range. In addition, when water is added at the start of storage, the water can be used as it is as water to be added during the reaction.
水に加えて、ポリオキシアルキレンアルキルエーテルを共存させてもよい。ポリオキシアルキレンアルキルエーテルを共存させる場合、その含有量は、におい悪化防止の観点より、保存される水溶液中１質量％以上が好ましく、２質量％以上がより好ましく、３質量％以上が更に好ましい。一方、次回の反応の濃度調製の観点より、５０質量％以下が好ましく、２５質量％以下がより好ましく、１５質量％以下がさらに好ましい。また、におい悪化の防止と、効率の観点から、ポリオキシアルキレンアルキルエーテルの含有量は１〜５０質量％が好ましく、２〜２５質量％がより好ましく、３〜１５質量％がさらに好ましい。 In addition to water, a polyoxyalkylene alkyl ether may coexist. In the case of coexisting polyoxyalkylene alkyl ether, the content thereof is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more in the stored aqueous solution, from the viewpoint of preventing odor deterioration. On the other hand, from the viewpoint of adjusting the concentration of the next reaction, it is preferably 50% by mass or less, more preferably 25% by mass or less, and further preferably 15% by mass or less. Moreover, 1-50 mass% is preferable from a viewpoint of prevention of an odor deterioration and efficiency, 1-50 mass% is more preferable, 2-25 mass% is more preferable, 3-15 mass% is further more preferable.
保存中の（Ａ）と（Ｂ）との接触頻度を少なくし、においの悪化を防止するためには、低温条件下で保存することも有効である。かかる観点より、保存時の温度は４０℃未満であり、３７℃未満に調整することが好ましい。しかし、過度に冷却することは溶液の粘度の上昇を招くため、保存時の温度は２０℃以上であり、２５℃以上に調整することが好ましい。また、取扱い性とにおい悪化防止の観点より、保存時の温度は２０℃〜４０℃未満であり、さらに２５℃〜３７℃未満に調整することが好ましい。 In order to reduce the frequency of contact between (A) and (B) during storage and prevent deterioration of odor, it is also effective to store under low temperature conditions. From this viewpoint, the temperature during storage is less than 40 ° C, and it is preferable to adjust the temperature to less than 37 ° C. However, since excessive cooling causes an increase in the viscosity of the solution, the temperature during storage is 20 ° C. or higher, and it is preferable to adjust to 25 ° C. or higher. Further, from the viewpoint of handling properties and prevention of odor deterioration, the temperature during storage is preferably 20 ° C to less than 40 ° C, and more preferably adjusted to 25 ° C to less than 37 ° C.
上記保存は、不活性ガス雰囲気で行うことが好ましい。不活性ガスとしては、窒素、アルゴン、ヘリウム、ネオン、クリプトン、キセノンなどを用いることができる。また、保存中は、触媒の沈降を防ぐために撹拌しておくことが好ましい。 The storage is preferably performed in an inert gas atmosphere. Nitrogen, argon, helium, neon, krypton, xenon, etc. can be used as the inert gas. In addition, during storage, it is preferable to stir to prevent the catalyst from settling.
上記保存期間としては特に限定されるものではないが、回分型反応器中で次回の反応に備えて保存する状況を考えると、通常は２４時間以上、３０日未満程度である。本発明の保存方法は、こうした保存期間中に反応容器内に残存する反応液のにおいの悪化を防止する効果を奏するが、この効果は保存が数日以上、例えば４日以上に及ぶ場合に顕著に表れる。 The storage period is not particularly limited, but is usually about 24 hours or longer and less than 30 days in consideration of the state of storage for the next reaction in a batch reactor. The preservation method of the present invention has an effect of preventing the deterioration of the odor of the reaction solution remaining in the reaction vessel during such a preservation period, but this effect is remarkable when the preservation takes several days or more, for example, four days or more. Appear in
本発明はまた、次の工程１〜５を繰り返す、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の製造方法を提供する。
工程１：反応容器内の水性媒体中で、貴金属触媒（Ｂ）の存在下に、ポリオキシアルキレンアルキルエーテルを酸素と接触させて酸化し、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）を含有する反応液を得る工程
工程２：工程１で得られた反応液の３０質量％以上、９０質量％以下を反応容器から抜き出す工程
工程３：工程２の後に、反応容器内に残留する反応液に水を加えてポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が５質量％以上、１５質量％以下の水溶液に調整する工程
工程４：前記水溶液を２０℃以上、４０℃未満の温度で保存する工程
工程５：工程２〜４のいずれかの後に、ポリオキシアルキレンアルキルエーテルを添加する工程
This invention also provides the manufacturing method of polyoxyalkylene alkyl ether acetate (A) which repeats the following processes 1-5.
Step 1: A reaction containing polyoxyalkylene alkyl ether acetate (A) in an aqueous medium in a reaction vessel in the presence of a noble metal catalyst (B) in contact with oxygen to oxidize the polyoxyalkylene alkyl ether acetate (A) Step 2: Obtain 30% by mass or more and 90% by mass or less of the reaction solution obtained in Step 1 Step 3: After Step 2, water is added to the reaction solution remaining in the reaction vessel. In addition, a step of adjusting the concentration of the polyoxyalkylene alkyl ether acetate (A) to an aqueous solution having a concentration of 5% by mass or more and 15% by mass or less: a step of storing the aqueous solution at a temperature of 20 ° C. or more and less than 40 ° C. 5: A step of adding polyoxyalkylene alkyl ether after any of steps 2 to 4
（工程１）
工程１はポリオキシアルキレンアルキルエーテルを酸素と接触させて、酸化する工程である。上に述べたように、一般式（２）のポリオキシアルキレンアルキルエーテル化合物を貴金属触媒（Ｂ）の存在下、酸素によって酸化することで、一般式（１）のポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）を得る。
(Process 1)
Step 1 is a step of oxidizing a polyoxyalkylene alkyl ether by contacting it with oxygen. As described above, the polyoxyalkylene alkyl ether compound of the general formula (2) is oxidized with oxygen in the presence of the noble metal catalyst (B), so that the polyoxyalkylene alkyl ether acetate salt of the general formula (1) ( A) is obtained.
工程１の水性媒体（液相）中のポリオキシアルキレンアルキルエーテルの濃度は、経済性の観点から５質量％以上が好ましく、１０質量％以上がより好ましい。また、反応液の粘度の観点から、３０質量％以下が好ましく、２５質量％以下がより好ましい。また、経済性と反応液の取扱い性の観点から、５〜３０質量％が好ましく、１０〜２５質量％がより好ましい。 The concentration of the polyoxyalkylene alkyl ether in the aqueous medium (liquid phase) in Step 1 is preferably 5% by mass or more and more preferably 10% by mass or more from the viewpoint of economy. Moreover, from a viewpoint of the viscosity of a reaction liquid, 30 mass% or less is preferable and 25 mass% or less is more preferable. Moreover, 5-30 mass% is preferable from a viewpoint of economical efficiency and the handleability of a reaction liquid, and 10-25 mass% is more preferable.
工程１において、貴金属触媒（Ｂ）は前述したものが用いられ、ポリオキシアルキレンアルキルエーテルに対して、反応速度の観点から０．１質量％以上となる量で用いることが好ましく、２％以上がより好ましい。経済性の観点より、貴金属触媒は２０質量％以下となる量で用いることが好ましく、１５質量％以下がより好ましい。また、反応性と経済性の観点から、質量比で０．１〜２０％となる量で用いることが好ましく、更に２〜１５％が好ましい。 In step 1, the above-mentioned noble metal catalyst (B) is used, and it is preferably used in an amount of 0.1% by mass or more, preferably 2% or more with respect to the polyoxyalkylene alkyl ether from the viewpoint of reaction rate. More preferred. From the economical viewpoint, the noble metal catalyst is preferably used in an amount of 20% by mass or less, more preferably 15% by mass or less. Moreover, it is preferable to use it in the quantity used as 0.1-20% by mass ratio from a reactive and economical viewpoint, and also 2-15% is preferable.
工程１は、酸性条件下、アルカリ性条件下のいずれにおいても可能であるが、反応速度の観点からアルカリ性条件下で行うことが好ましい。このとき用いるアルカリ物質としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩等が挙げられるが、なかでも、アルカリ金属水酸化物が好ましい。アルカリ物質は、液相のｐＨが９〜１４となるような量で用いることが好ましい。 Step 1 can be performed under acidic conditions or alkaline conditions, but is preferably performed under alkaline conditions from the viewpoint of reaction rate. Examples of the alkali substance used at this time include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Among them, alkali metal hydroxides are preferable. . The alkaline substance is preferably used in such an amount that the pH of the liquid phase is 9-14.
工程１で用いる酸素としては、前述のように空気などの種々の酸素含有気体を用いることができるが、反応速度の観点から酸素濃度８０％〜１００％のものが好ましい。 As oxygen used in Step 1, various oxygen-containing gases such as air can be used as described above, but those having an oxygen concentration of 80% to 100% are preferable from the viewpoint of reaction rate.
工程１における反応温度としては、円滑に反応を進める観点から、４０℃以上が好ましく、５０℃以上がより好ましい。また、におい悪化防止の観点から８０℃以下が好ましく、７０℃以下がより好ましい。また、反応性とにおい劣化防止の観点から４０〜８０℃、更に５０〜７０℃が好ましい。 The reaction temperature in step 1 is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of smoothly proceeding the reaction. Moreover, 80 degrees C or less is preferable from a viewpoint of odor deterioration prevention, and 70 degrees C or less is more preferable. Moreover, 40-80 degreeC and 50-70 degreeC are more preferable from a viewpoint of reactivity and prevention of odor deterioration.
工程１における反応圧力としては、酸素の反応液への溶解度を高める観点から絶対圧力として０．０５ＭＰａ以上が好ましく、０．１ＭＰａ（常圧）以上がより好ましい。また、装置の耐圧性の観点から、１．０ＭＰａ以下が好ましく、０．５ＭＰａ以下がより好ましい。また酸素の反応液への溶解度を高める観点及び装置の耐圧性の観点から、絶対圧力として０．０５〜１．０ＭＰａが好ましく、０．１（常圧）〜０．５ＭＰａがより好ましい。 The reaction pressure in step 1 is preferably 0.05 MPa or more, more preferably 0.1 MPa (normal pressure) or more as an absolute pressure from the viewpoint of increasing the solubility of oxygen in the reaction solution. Further, from the viewpoint of pressure resistance of the apparatus, 1.0 MPa or less is preferable, and 0.5 MPa or less is more preferable. Further, from the viewpoint of increasing the solubility of oxygen in the reaction solution and from the viewpoint of pressure resistance of the apparatus, the absolute pressure is preferably 0.05 to 1.0 MPa, more preferably 0.1 (normal pressure) to 0.5 MPa.
工程１においては、攪拌槽型反応器を用いて液相を撹拌しながらポリオキシアルキレンアルキルエーテルの酸素酸化を行う。液相の撹拌は、例えば三枚後退翼、フルゾーン翼、タービン翼、マックスブレンド翼等の攪拌翼を備えた攪拌機により行うことができる。 In step 1, the oxygen oxidation of the polyoxyalkylene alkyl ether is carried out while stirring the liquid phase using a stirred tank reactor. The liquid phase can be stirred by a stirrer equipped with a stirring blade such as a three-blade retreating blade, a full zone blade, a turbine blade, or a max blend blade.
工程１において、ポリオキシアルキレンアルキルエーテル、アルカリ物質、水、貴金属触媒（Ｂ）はそれぞれ、連続的もしくは断続的に、反応器に仕込むことができる。アルカリ物質は一般に水溶液として使用できるが、この仕込み方法としては、液相のｐＨが所定の値を維持するよう、連続的又は断続的に仕込んでもよい。 In Step 1, the polyoxyalkylene alkyl ether, the alkaline substance, water, and the noble metal catalyst (B) can be charged into the reactor continuously or intermittently, respectively. In general, the alkaline substance can be used as an aqueous solution. However, as the charging method, the alkaline phase may be charged continuously or intermittently so that the pH of the liquid phase is maintained at a predetermined value.
（工程２）
工程２は工程１で得られたポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）を含有する反応液の３０質量％以上、９０質量％以下を反応容器から抜き出す工程である。
(Process 2)
Step 2 is a step of extracting 30% by mass or more and 90% by mass or less of the reaction solution containing the polyoxyalkylene alkyl ether acetate (A) obtained in Step 1 from the reaction vessel.
１バッチ当たりの出来高を高める観点から、工程２の抜き出し量を全反応液の３０質量％以上とすることが好ましく、４０質量％以上とすることがより好ましく、５０質量％以上とすることが更に好ましい。また、粘度を低く制御して１バッチ当たりの反応時間を短くする観点から、工程２の抜出量を全反応液の９０質量％以下とすることが好ましく、８０質量％以下とすることがより好ましく、７０質量％以下とすることが更に好ましい。また、高い生産性を確保するためには、工程２の抜き出し量を全反応液の３０〜９０質量％とすることが好ましく、４０〜８０質量％とすることがより好ましく、５０〜７０質量％とすることがさらに好ましい。 From the viewpoint of increasing the output per batch, the amount of extraction in step 2 is preferably 30% by mass or more of the total reaction solution, more preferably 40% by mass or more, and further preferably 50% by mass or more. preferable. Moreover, from the viewpoint of controlling the viscosity to be low and shortening the reaction time per batch, it is preferable to set the withdrawal amount in step 2 to 90% by mass or less, more preferably to 80% by mass or less of the total reaction solution. Preferably, it is more preferable to set it as 70 mass% or less. Moreover, in order to ensure high productivity, it is preferable to make the extraction amount of the process 2 into 30-90 mass% of all the reaction liquids, It is more preferable to set it as 40-80 mass%, 50-70 mass% More preferably.
抜き出した反応液からは、ろ過によって、貴金属触媒（Ｂ）を除くことができる。除いた貴金属触媒（Ｂ）は、そのまま、あるいは活性化処理の後、反応槽にもどして次の反応に用いることができる。 The noble metal catalyst (B) can be removed from the extracted reaction solution by filtration. The removed noble metal catalyst (B) can be used in the next reaction as it is or after being activated and returned to the reaction vessel.
ろ過後の触媒を除いた液相には、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）が溶解しているので、ｐＨ調整をした後、そのまま界面活性剤溶液として使用するか、或いは、塩酸等の鉱酸で酸分解して抽出工程を経て、遊離のカルボン酸を得ることができる。 Since the polyoxyalkylene alkyl ether acetate (A) is dissolved in the liquid phase after removal of the catalyst after filtration, the pH is adjusted and then used as a surfactant solution as it is, or hydrochloric acid or the like Free carboxylic acid can be obtained through acid extraction with a mineral acid and an extraction step.
（工程３）
工程３は、反応容器内に残留する反応液に水を加えてポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が５質量％以上、１５質量％以下の水溶液に調整する工程である。
(Process 3)
Step 3 is a step of adding water to the reaction solution remaining in the reaction vessel to adjust the concentration of the polyoxyalkylene alkyl ether acetate (A) to an aqueous solution having a concentration of 5% by mass to 15% by mass.
工程３において、添加する水の量は、におい悪化防止の観点から、添加後のポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が１５質量％以下になるように加える。添加する水の量は、同様の観点から、添加後のポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が１３質量％以下になるようにすることが好ましい。また、添加する水の量は、経済性の観点から、添加後のポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が５質量％以上になるように加える。添加する水の量は、同様の観点から、添加後のポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が７質量％以上になるようにすることが好ましい。また経済性と品質の観点から、添加する水の量は、添加後のポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が５〜１５質量％になる量であり、７〜１３質量％になる量が好ましい。 In step 3, the amount of water to be added is added so that the concentration of the polyoxyalkylene alkyl ether acetate (A) after addition is 15% by mass or less from the viewpoint of preventing odor deterioration. From the same viewpoint, the amount of water to be added is preferably such that the concentration of the polyoxyalkylene alkyl ether acetate (A) after addition is 13% by mass or less. The amount of water to be added is added so that the concentration of the polyoxyalkylene alkyl ether acetate (A) after addition is 5% by mass or more from the viewpoint of economy. From the same viewpoint, the amount of water added is preferably such that the concentration of the polyoxyalkylene alkyl ether acetate (A) after addition is 7% by mass or more. From the viewpoint of economy and quality, the amount of water to be added is such that the concentration of the polyoxyalkylene alkyl ether acetate (A) after addition is 5 to 15% by mass, and 7 to 13% by mass. An amount is preferred.
（工程４）
工程４は、工程３の水溶液を２０℃以上、４０℃未満の温度で保存する工程である。工程４における保存温度は、品質の観点および粘度の観点から、２０℃以上、４０℃未満であり、２５℃以上、３７℃未満が好ましい。なお温度調整は工程３の前に行ってもよく、また工程３と同時に行ってもよい。
(Process 4)
Step 4 is a step of storing the aqueous solution of step 3 at a temperature of 20 ° C. or higher and lower than 40 ° C. The storage temperature in Step 4 is 20 ° C. or more and less than 40 ° C., and preferably 25 ° C. or more and less than 37 ° C. from the viewpoint of quality and viscosity. The temperature adjustment may be performed before step 3 or may be performed simultaneously with step 3.
工程４は、不活性ガス雰囲気で行うことが好ましい。不活性ガスとしては、窒素、アルゴン、ヘリウム、ネオン、クリプトン、キセノンなどを用いることができる。また保存中は、触媒の沈降を防ぐために反応容器内の水溶液を適宜撹拌しておくことが好ましい。 Step 4 is preferably performed in an inert gas atmosphere. Nitrogen, argon, helium, neon, krypton, xenon, etc. can be used as the inert gas. During storage, the aqueous solution in the reaction vessel is preferably agitated as appropriate in order to prevent the catalyst from settling.
工程４における保存期間としては特に限定されるものではないが、通常は４時間以上、３０日未満程度である。本発明の保存方法は、こうした保存期間中に反応容器内に残存する反応液のにおいの悪化を防止する効果を奏するが、この効果は保存が数日以上、例えば４日以上に及ぶ場合に顕著に表れる。 Although it does not specifically limit as a preservation | save period in the process 4, Usually, it is about 4 hours or more and less than about 30 days. The preservation method of the present invention has an effect of preventing the deterioration of the odor of the reaction solution remaining in the reaction vessel during such a preservation period, but this effect is remarkable when the preservation takes several days or more, for example, four days or more. Appear in
（工程５）
工程５は工程２〜４のいずれかの後に、ポリオキシアルキレンアルキルエーテルを添加する工程である。その添加量は、次いで行われる工程１のポリオキシアルキレンアルキルエーテルの添加量以下となる量であればよく、添加後のポリオキシアルキレンアルキルエーテル含有量が、におい悪化防止の観点と、次回の反応の濃度調製の観点から、１〜５０質量％となる添加量が好ましく、２〜２５質量％となる添加量がより好ましく、３〜１５質量％となる添加量がさらに好ましい。
(Process 5)
Step 5 is a step of adding polyoxyalkylene alkyl ether after any of Steps 2 to 4. The addition amount may be an amount that is equal to or less than the addition amount of the polyoxyalkylene alkyl ether in Step 1 to be performed next, and the content of the polyoxyalkylene alkyl ether after the addition is the next reaction. From the viewpoint of adjusting the concentration, the addition amount of 1 to 50% by mass is preferable, the addition amount of 2 to 25% by mass is more preferable, and the addition amount of 3 to 15% by mass is more preferable.
工程５の実施は工程２〜工程４のあいだならどこで行ってもよいが、粘度の観点から工程３、工程４、工程５をこの順で行うことが好ましい。工程３と工程４の間に行う場合、工程５の実施後の反応容器内の水溶液中のポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が５質量％以上、１５質量％以下であるように行う必要がある。 Implementation of step 5 may be performed anywhere between step 2 and step 4, but from the viewpoint of viscosity, step 3, step 4, and step 5 are preferably performed in this order. When performing between Step 3 and Step 4, the concentration of polyoxyalkylene alkyl ether acetate (A) in the aqueous solution in the reaction vessel after Step 5 is 5% by mass or more and 15% by mass or less. There is a need to do.
これらの工程を繰り返すことで、ポリオキシアルキレンアルキルエーテル酢酸塩の製造中に反応液を反応槽に残留した触媒と接触させたまま保存又は待機するような場合に、製品のにおいが悪化する問題を回避することができ、においの少ないポリオキシアルキレンアルキルエーテル酢酸塩を効率よく得ることができる。 By repeating these steps, there is a problem that the odor of the product deteriorates when the reaction solution is stored or kept in contact with the catalyst remaining in the reaction vessel during the production of the polyoxyalkylene alkyl ether acetate. It can be avoided and a polyoxyalkylene alkyl ether acetate salt with less odor can be obtained efficiently.
実施例１
１Ｌステンレス製容器に、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）として濃度２０質量％のポリオキシエチレンドデシルエーテル酢酸ナトリウム（平均ＥＯ付加モル数２．５）水溶液５４２．９３ｇ、貴金属触媒（Ｂ）としてＰｄ−Ｐｔ−Ｂｉ／Ｃ触媒（含水率５８．３質量％）１３．２ｇ、水５５８．９７ｇを加え、濃度１０質量％のポリオキシエチレンドデシルエーテル酢酸ナトリウム、触媒混合水溶液とした。この水溶液をマグネティックスターラーで撹拌しながら、窒素雰囲気下、３５℃で保存した。保存開始後１４日目のにおいを確認したところ、保存開始時と変化がなかった。
また、１４日目の保存液２５５．８４ｇにポリオキシエチレンドデシルエーテル（含水率６．５質量％）３８．５０ｇ、４８％ＮａＯＨ８．７０ｇを加えて、６０℃で酸素を反応液内に流通させポリオキシエチレンドデシルエーテル酢酸塩水溶液を得た。ろ過後にこのエーテル酢酸水溶液の官能評価（におい評価）を行ったところ、工程１の方法で製造された通常のポリオキシエチレンドデシルエーテル酢酸ナトリウム（平均ＥＯ付加モル数２．５）水溶液と同程度であった。
Example 1
In a 1 L stainless steel container, as a polyoxyalkylene alkyl ether acetate (A), a polyoxyethylene dodecyl ether sodium acetate (average EO addition mole number 2.5) aqueous solution 542.93 g of 20% by mass, as a noble metal catalyst (B) 13.2 g of Pd—Pt—Bi / C catalyst (water content: 58.3% by mass) and 558.97 g of water were added to obtain a polyoxyethylene dodecyl ether sodium acetate / catalyst mixed aqueous solution having a concentration of 10% by mass. The aqueous solution was stored at 35 ° C. under a nitrogen atmosphere while stirring with a magnetic stirrer. When the smell on the 14th day after the start of storage was confirmed, there was no change from the start of storage.
In addition, 38.50 g of polyoxyethylene dodecyl ether (water content 6.5% by mass) and 8.70 g of 48% NaOH were added to 255.84 g of the stock solution on the 14th day, and oxygen was circulated in the reaction solution at 60 ° C. A polyoxyethylene dodecyl ether acetate aqueous solution was obtained. When the sensory evaluation (smell evaluation) of this ether acetic acid aqueous solution was performed after filtration, it was almost the same as a normal polyoxyethylene dodecyl ether sodium acetate (average EO addition mole number 2.5) aqueous solution produced by the method of Step 1. there were.
比較例
１Ｌステンレス製容器に、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）として濃度２０質量％のポリオキシエチレンドデシルエーテル酢酸ナトリウム（平均ＥＯ付加モル数２．５）水溶液１１７２．０８ｇ、貴金属触媒（Ｂ）としてＰｄ−Ｐｔ−Ｂｉ／Ｃ触媒（含水率５８．３質量％）２８．５０ｇを加え、濃度２０質量％のポリオキシエチレンドデシルエーテル酢酸ナトリウム、触媒混合水溶液とした。この水溶液を、マグネティックスターラーで撹拌しながら、窒素雰囲気下、４０℃で保存した。保存開始後４日目のにおいを確認したところ、保存開始時よりもにおいが悪化していた。
また、４日目の保存液１２０．００ｇにポリオキシエチレンドデシルエーテル（含水率６．５質量％）３８．６２ｇ、４８％ＮａＯＨ８．７０ｇ、水１２９．４７ｇを加えて、６０℃で酸素を反応液内に流通させポリオキシエチレンドデシルエーテル酢酸塩水溶液を得た。ろ過後にこのエーテル酢酸水溶液の官能評価（におい評価）を行ったところ、工程１の方法で製造された通常のポリオキシエチレンドデシルエーテル酢酸ナトリウム（平均ＥＯ付加モル数２．５）水溶液よりもにおいが悪化していた。
Comparative Example In a 1 L stainless steel container, 1172.08 g of an aqueous solution of polyoxyethylene dodecyl ether sodium acetate (average EO addition mole number 2.5) having a concentration of 20% by mass as polyoxyalkylene alkyl ether acetate (A), noble metal catalyst (B ) Was added 28.50 g of a Pd—Pt—Bi / C catalyst (moisture content: 58.3% by mass) to prepare a polyoxyethylene dodecyl ether sodium acetate / catalyst mixed aqueous solution having a concentration of 20% by mass. This aqueous solution was stored at 40 ° C. under a nitrogen atmosphere while stirring with a magnetic stirrer. When the smell on the fourth day after the start of storage was confirmed, the smell was worse than that at the start of storage.
Moreover, 38.62 g of polyoxyethylene dodecyl ether (water content 6.5 mass%), 8.70 g of 48% NaOH, and 129.47 g of water were added to 120.00 g of the preservation solution on the fourth day, and oxygen was reacted at 60 ° C. A polyoxyethylene dodecyl ether acetate aqueous solution was obtained by circulating in the liquid. When the sensory evaluation (odor evaluation) of this ether acetic acid aqueous solution was performed after filtration, it smelled more than the normal polyoxyethylene dodecyl ether sodium acetate (average EO addition mole number 2.5) aqueous solution produced by the method of Step 1. It was getting worse.
評価方法
実施例及び比較例で得られた各エーテル酢酸水溶液５０ｇを１００ｍＬスクリュー管に入れ、パネラー（健常者）４人による瓶口での官能評価（臭い評価）を行った。官能評価は下記に示す０〜５の６段階の数値にて評価を行い、４人の平均値で示した。結果を表１に示す。なお、工程１の方法で製造されたポリオキシエチレンドデシルエーテル酢酸ナトリウム（平均ＥＯ付加モル数２．５）水溶液を本手法で評価すると２．５であった。
Evaluation method 50 g of each ether acetic acid aqueous solution obtained in Examples and Comparative Examples was put into a 100 mL screw tube, and sensory evaluation (odor evaluation) was performed at the bottle mouth by four panelists (healthy persons). The sensory evaluation was carried out with the following six values from 0 to 5, and the average value of four people was shown. The results are shown in Table 1. In addition, it was 2.5 when the polyoxyethylene dodecyl ether sodium acetate (average EO addition mole number 2.5) aqueous solution manufactured by the method of the process 1 was evaluated by this method.
＜臭いの評価基準＞
０：無臭
１：判別できない弱い臭い
２：弱いが判別可能な臭い
３：明らかにわかる臭い
４：強い臭い
５：強烈な臭い
<Odor evaluation criteria>
0: odorless 1: weak odor that cannot be distinguished 2: weak odor that can be distinguished 3: clear odor 4: strong odor 5: intense odor
Claims (8)
工程１：反応容器内の水性媒体中で、貴金属触媒（Ｂ）の存在下に、ポリオキシアルキレンアルキルエーテルを酸素と接触させて酸化し、ポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）を含有する反応液を得る工程
工程２：工程１で得られた反応液の３０質量％以上、９０質量％以下を反応容器から抜き出す工程
工程３：工程２の後に、反応容器内に残留する反応液に水を加えてポリオキシアルキレンアルキルエーテル酢酸塩（Ａ）の濃度が５質量％以上、１５質量％以下の水溶液に調整する工程
工程４：前記水溶液を不活性ガス雰囲気下に２０℃以上、４０℃未満の温度で保存する工程
工程５：工程２〜４のいずれかの後に、ポリオキシアルキレンアルキルエーテルを添加する工程 The manufacturing method of polyoxyalkylene alkyl ether acetate (A) containing the following processes 1-5.
Step 1: A reaction containing polyoxyalkylene alkyl ether acetate (A) in an aqueous medium in a reaction vessel in the presence of a noble metal catalyst (B) in contact with oxygen to oxidize the polyoxyalkylene alkyl ether acetate (A) Step 2: Obtain 30% by mass or more and 90% by mass or less of the reaction solution obtained in Step 1 Step 3: After Step 2, water is added to the reaction solution remaining in the reaction vessel. In addition, the step of adjusting the concentration of the polyoxyalkylene alkyl ether acetate (A) to an aqueous solution having a concentration of 5% by mass or more and 15% by mass or less: Step 4: The aqueous solution is 20 ° C. or more and less than 40 ° C. in an inert gas atmosphere . Step 5 of storing at temperature Step: Step of adding polyoxyalkylene alkyl ether after any of steps 2 to 4
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