JPH075511B2 - Method for producing carboxylate - Google Patents
Method for producing carboxylateInfo
- Publication number
- JPH075511B2 JPH075511B2 JP61041113A JP4111386A JPH075511B2 JP H075511 B2 JPH075511 B2 JP H075511B2 JP 61041113 A JP61041113 A JP 61041113A JP 4111386 A JP4111386 A JP 4111386A JP H075511 B2 JPH075511 B2 JP H075511B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- component
- reaction
- present
- palladium
- 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 - Lifetime
Links
- 150000007942 carboxylates Chemical class 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 229910052714 tellurium Inorganic materials 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 150000001734 carboxylic acid salts Chemical class 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- -1 carboxylate salt Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000000774 hypoallergenic effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Polyethers (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は一般式(1)で表される化合物 RO(EO)nH (1) （以後、化合物(1)と呼ぶ。但し、EOはエチレンオキシ
ド、Ｒは炭素数４〜14の直鎖又は又は分岐のアルキル基
を有するアルキルフェニル基、又は炭素数８〜36の直鎖
又は分岐のアルキル基、もしくはアルケニル基を示し、
ｎは１〜100の整数を示す） の末端一級水酸基を酸化することによる相当するカルボ
ン酸塩の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a compound represented by the general formula (1): RO (EO) n H (1) (hereinafter referred to as compound (1). Ethylene oxide, R represents an alkylphenyl group having a linear or branched alkyl group having 4 to 14 carbon atoms, or a linear or branched alkyl group having 8 to 36 carbon atoms, or an alkenyl group,
n represents an integer of 1 to 100) and a method for producing a corresponding carboxylate by oxidizing a terminal primary hydroxyl group.
更に詳しくは一般式(1)で表される化合物を本発明の特
別な触媒の存在下に接触酸化することにより、一般式
(2)で表される相当するカルボン酸塩 RO(EO)n-1-CH2COOX (2) （以後、カルボン酸塩(2)と呼ぶ。但し、EO,Rおよびｎ
は、一般式(1)で表される化合物におけるのと同一の意
味であり、Ｘはアルカリ金属を示す） を高収率で製造する方法に関する。More specifically, by subjecting the compound represented by the general formula (1) to catalytic oxidation in the presence of the special catalyst of the present invention, the general formula
Corresponding carboxylate salt represented by (2) RO (EO) n-1 -CH 2 COOX (2) (hereinafter referred to as carboxylate salt (2), provided that EO, R and n
Has the same meaning as in the compound represented by the general formula (1), and X represents an alkali metal) in a high yield.
上記一般式(2)で表されるカルボン酸塩は低刺激性で、
且つ耐硬水性のある優れたアニオン界面活性剤である。The carboxylic acid salt represented by the general formula (2) is hypoallergenic,
It is also an excellent anionic surfactant having hard water resistance.
従来このカルボン酸塩は、化合物(1)とモノクロル酢酸
ソーダを苛性ソーダの存在下に反応させて製造されてい
るが、収率は70〜75％である。又、下式からも明らかな
ように、モノクロル酢酸ソーダを用いる従来の方法では
等モルの塩化ナトリウムが副生する欠点がある。This carboxylic acid salt is conventionally produced by reacting the compound (1) with sodium monochloroacetate in the presence of caustic soda, and the yield is 70 to 75%. Further, as is apparent from the following formula, the conventional method using sodium monochloroacetate has a drawback that equimolar sodium chloride is by-produced.
従って、この副生塩化ナトリウムの為に反応生成物の粘
度が上昇し作業性が悪くなるのみならず、家庭用液体洗
浄剤の原料として利用した場合、副生塩化ナトリウムの
為に悪影響が出る場合がある。 Therefore, not only does this by-product sodium chloride increase the viscosity of the reaction product and worsen the workability, but when it is used as a raw material for household liquid cleaners, the by-product sodium chloride causes adverse effects. There is.
従って、低刺激性、耐硬水性等の優れた性質を有するカ
ルボン酸塩(2)を高収率で、且つ塩化ナトリウムが副生
しないように合成することは極めて有用である。Therefore, it is extremely useful to synthesize the carboxylic acid salt (2) having excellent properties such as low irritation and hard water resistance in a high yield and without producing sodium chloride as a by-product.
以上の問題点を解決するため、一般式(1)で表される化
合物 RO(EO)nH (1) （但し、EOはエチレンオキシド、Ｒは炭素数４〜14の直
鎖又は分岐のアルキル基を有するアルキルフェニル基、
又は炭素数８〜36の直鎖又は分岐のアルキル基、もしく
はアルケニル基を示し、ｎは１〜100の整数を示す） をパラジウム触媒の存在下接触酸化して、目的とするカ
ルボン酸塩を製造する方法が提案（特開昭53−141218
号）されている。In order to solve the above problems, a compound represented by the general formula (1) RO (EO) n H (1) (where EO is ethylene oxide, R is a linear or branched alkyl group having 4 to 14 carbon atoms) An alkylphenyl group having
Or a linear or branched alkyl group having 8 to 36 carbon atoms, or an alkenyl group, and n is an integer of 1 to 100) is subjected to catalytic oxidation in the presence of a palladium catalyst to produce a desired carboxylate. A method is proposed (Japanese Patent Laid-open No.
No.).
RO(EO)nH→RO(EO)n-1-CH2COOX しかるに特開昭53−141218号の明細書に記載されている
方法では、目的とするカルボン酸塩(2)が高々80％の収
率でしか得られず、まだ満足のいく方法ではないと言え
る。RO (EO) n H → RO (EO) n-1 -CH 2 COOX However, in the method described in JP-A-53-141218, the desired carboxylate (2) is at most 80%. It can be said that it is not a satisfactory method because it is obtained only in the yield of.
そこで本発明者等は化合物(1)を高収率で目的とするカ
ルボン酸塩(2)に酸化すべく鋭意検討した結果、本発明
に到達した。Therefore, the present inventors have arrived at the present invention as a result of extensive studies to oxidize the compound (1) into the desired carboxylate (2) in high yield.
即ち、本発明は一般式(1)で表される化合物 RO(EO)nH (1) （但し、EOはエチレンオキシド、Ｒは炭素数４〜14の直
鎖又は又は分岐のアルキル基を有するアルキルフェニル
基、又は炭素数８〜36の直鎖又は分岐のアルキル基、も
しくはアルケニル基を示し、ｎは１〜100の整数を示
す） を水溶媒系で、反応温度30〜100℃、反応圧10気圧まで
の条件下、パラジウムを触媒第１成分とし、セレン、テ
ルル、スズおよびビスマスから成る群から選ばれる１種
以上を触媒第２成分として含有し、触媒第２成分と第１
成分の比率（原子比）が0.01〜2.0であり、予め触媒第
１成分と触媒第２成分とを担体に担持させた担持触媒の
存在下、反応系のpHを7.5以上に調節しながら酸素もし
くは酸素含有ガスで接触酸化することを特徴とする一般
式(2)で表される相当するカルボン酸塩の製造法を提供
するものである。That is, the present invention relates to a compound represented by the general formula (1) RO (EO) n H (1) (wherein EO is ethylene oxide, R is an alkyl group having a linear or branched alkyl group having 4 to 14 carbon atoms). A phenyl group, or a linear or branched alkyl group having 8 to 36 carbon atoms, or an alkenyl group, and n represents an integer of 1 to 100) in an aqueous solvent system at a reaction temperature of 30 to 100 ° C. and a reaction pressure of 10 Under conditions up to atmospheric pressure, palladium is used as the catalyst first component, and at least one selected from the group consisting of selenium, tellurium, tin and bismuth is contained as the catalyst second component, and the catalyst second component and the first component are included.
The ratio (atomic ratio) of the components is 0.01 to 2.0, and oxygen or oxygen is added while adjusting the pH of the reaction system to 7.5 or more in the presence of a supported catalyst in which the catalyst first component and the catalyst second component are previously supported on the carrier. The present invention provides a method for producing a corresponding carboxylic acid salt represented by the general formula (2), which is characterized by catalytic oxidation with an oxygen-containing gas.
本発明の特別な触媒を用いて化合物(1)を酸化すると、9
0％以上の収率で目的とするカルボン酸塩(2)に変換され
る。Oxidation of compound (1) with the special catalyst of the present invention gives 9
It is converted to the desired carboxylate (2) with a yield of 0% or more.
本発明の触媒においては、触媒第２成分と第１成分の比
率（第２成分／第１成分）が原子比で0.01〜2.0の範囲
内にあることが特に重要であり、この範囲から外れると
本発明の効果が得られない。In the catalyst of the present invention, it is particularly important that the ratio of the second component of the catalyst to the first component (second component / first component) is within the range of 0.01 to 2.0 in atomic ratio. The effect of the present invention cannot be obtained.
本発明において使用する触媒は、担持触媒として使用さ
れる。担体としては、一般に公知のものが使用される。
例えば、活性炭、石綿、シリカ、活性白土もしくはアル
ミナ等が挙げられるが、中でも特に活性炭が好ましい。
また触媒第１成分および第２成分の担持量は通常それぞ
れ0.5〜20重量％、0.01〜20重量％、好ましくはそれぞ
れ３〜12重量％、0.1〜12重量％である。The catalyst used in the present invention is used as a supported catalyst. As the carrier, generally known carriers are used.
For example, activated carbon, asbestos, silica, activated clay, alumina or the like can be mentioned, but activated carbon is particularly preferable.
The supported amounts of the first component and the second component of the catalyst are usually 0.5 to 20% by weight, 0.01 to 20% by weight, and preferably 3 to 12% by weight and 0.1 to 12% by weight, respectively.
さらに、本発明の触媒にシリカ、アルカリ土類元素、亜
鉛あるいは遷移金属等の化合物を添加することにより、
触媒の耐久性の向上、活性の向上あるいは酸化生成物で
あるカルボン酸塩(2)の色相等が向上をもたらす場合が
ある。Furthermore, by adding a compound such as silica, an alkaline earth element, zinc or a transition metal to the catalyst of the present invention,
In some cases, the durability of the catalyst may be improved, the activity may be improved, or the hue of the carboxylate (2) as an oxidation product may be improved.
本発明に用いられる触媒は公知の方法で予め調製され
る。例えば、触媒第１成分、第２成分がそれぞれパラジ
ウム、テルル、触媒担体が活性炭である本発明の触媒を
調製するには、まず活性炭をイオン交換水中に分散させ
る。この場合、使用する活性炭は常法に従って精製する
ことにより触媒活性が向上することがある。一方、触媒
第１成分および第２成分の原料として塩化パラジウムお
よび酸化テルルを選びそれらの塩酸水溶液を調製し、常
法に従って先に調製した活性炭に吸着させる。吸着後は
ホルマリン、ヒドラジン、ソジウムボロハイドライド、
水素等で加熱下に還元処理を行う。還元終了後、触媒を
濾別する。以上の方法によって、本発明で使用する触媒
が得られるが、触媒は乾燥することなく含水状態のまま
反応に使用することが出来る。The catalyst used in the present invention is prepared in advance by a known method. For example, in order to prepare the catalyst of the present invention in which the first component and the second component of the catalyst are palladium and tellurium, respectively, and the catalyst carrier is activated carbon, activated carbon is first dispersed in ion-exchanged water. In this case, the activated carbon used may be improved in catalytic activity by being purified according to a conventional method. On the other hand, palladium chloride and tellurium oxide are selected as raw materials for the first component and the second component of the catalyst to prepare an aqueous hydrochloric acid solution thereof, and the activated carbon prepared above is adsorbed by a conventional method. After adsorption, formalin, hydrazine, sodium borohydride,
The reduction treatment is performed with heating with hydrogen or the like. After the reduction is completed, the catalyst is filtered off. By the above method, the catalyst used in the present invention can be obtained, but the catalyst can be used for the reaction in a water-containing state without being dried.
本発明の触媒を用いて化合物(1)を酸化するにあたり、
酸化反応に有利なpH7.5以上で、水溶媒系で実施する。
即ち、酸化反応の進行と共に反応系のpHが低下するた
め、苛性アルカリを添加して中和しながら酸化反応を進
行させるのが良い。苛性アルカリとしては苛性ソーダも
しくは苛性カリがよい。苛性アルカリの添加量は理論的
には酸化される化合物(1)と等モルでよいが、数％過剰
に仕込む方が好結果を与えることがある。苛性アルカリ
は一般に水溶液として使用するが、この仕込み方法とし
ては、反応初期に一括仕込みするか、あるいは反応系の
pH7.5以上の範囲内で適当なpHに維持するよう、連続も
しくは断続的に仕込んでもよい。In oxidizing the compound (1) using the catalyst of the present invention,
It is carried out in an aqueous solvent system at a pH of 7.5 or higher, which is favorable for the oxidation reaction.
That is, since the pH of the reaction system decreases with the progress of the oxidation reaction, it is preferable to proceed with the oxidation reaction while adding caustic to neutralize. The caustic alkali is preferably caustic soda or caustic potash. The addition amount of the caustic may theoretically be equimolar to the compound (1) to be oxidized, but it may give better results by adding a few% excess. Caustic alkali is generally used as an aqueous solution, and this charging method may be carried out by batch charging at the beginning of the reaction or by the reaction system.
It may be continuously or intermittently charged so as to maintain an appropriate pH within the range of pH 7.5 or higher.
酸化反応は一般に高pHの方が反応速度が大であるが、酸
化反応生成物であるカルボン酸塩(2)の色相の点で、pH8
〜10で実施するのがよい。The oxidation reaction generally has a higher reaction rate at a higher pH, but in terms of the hue of the carboxylate (2) which is an oxidation reaction product, a pH of 8
It is better to carry out at ~ 10.
この際、化合物(1)の濃度は11〜40重量％、好ましくは1
5〜25重量％がよい。化合物(1)の構造によってはHLBの
関係で反応初期、均一水溶液にならない場合があるが、
酸化反応の進行とともに相当するカルボン酸塩(2)が生
成し、反応系は反応の進行と共に均一になるので問題は
ない。酸化反応時使用する本発明触媒の第１成分と第２
成分を合わせた添加量は化合物(1)に対して0.05〜10重
量％、好ましくは0.1〜５重量％である。At this time, the concentration of the compound (1) is 11 to 40% by weight, preferably 1
5-25% by weight is good. Depending on the structure of compound (1), it may not be a homogeneous aqueous solution at the initial stage of the reaction due to HLB,
There is no problem because the corresponding carboxylic acid salt (2) is produced as the oxidation reaction progresses and the reaction system becomes homogeneous as the reaction progresses. The first component and the second component of the catalyst of the present invention used in the oxidation reaction
The total amount of the components added is 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the compound (1).
反応温度は30〜100℃、好ましくは40〜80℃がよい。The reaction temperature is 30 to 100 ° C, preferably 40 to 80 ° C.
酸化反応に使用する酸化剤として通常酸素ガスを使用す
るが、酸素を窒素で希釈した酸素含有ガスもしくは空気
を使用することも出来る。Oxygen gas is usually used as the oxidant used in the oxidation reaction, but an oxygen-containing gas obtained by diluting oxygen with nitrogen or air can also be used.
酸化反応時の反応圧力は10気圧までが良く、好ましくは
常圧がよい。The reaction pressure during the oxidation reaction is preferably up to 10 atm, preferably normal pressure.
また、本発明の触媒組成物を用いる化合物(1)の接触酸
化反応は回分式もしくは連続式で実施される。Further, the catalytic oxidation reaction of the compound (1) using the catalyst composition of the present invention is carried out batchwise or continuously.
本発明の触媒を用いて化合物(1)を酸化するには一般に
次のように行う。Oxidation of compound (1) using the catalyst of the present invention is generally performed as follows.
ガス導入口、ガス出口、温度計、サンプリング口および
攪拌器のついたフラスコに、化合物(1)の20％水溶液も
しくは乳化液（HLBの関係で反応前は乳化状態になって
いる場合がある）および、本発明の触媒及び化合物(1)
に対して約1.05倍モル等量の48％苛性ソーダを仕込む。In a flask equipped with a gas inlet, gas outlet, thermometer, sampling port and stirrer, a 20% aqueous solution or emulsion of compound (1) (may be in an emulsified state before the reaction due to HLB). And the catalyst and compound (1) of the present invention
About 1.05 times the molar equivalent of 48% caustic soda is charged.
攪拌下75℃まで昇温し、酸素ガスを常圧で、ガス導入口
から反応系にバブリング導入する。酸化反応は円滑に進
行し数時間で反応は終了する。反応終了後冷却し、濾過
によって触媒と生成物を分離する。The temperature is raised to 75 ° C. with stirring, and oxygen gas is bubbled into the reaction system at atmospheric pressure from the gas inlet. The oxidation reaction proceeds smoothly, and the reaction ends in a few hours. After completion of the reaction, the mixture is cooled and the catalyst and the product are separated by filtration.
生成物は、pH調製をした後界面活性剤溶液として使用す
るか、あるいは塩酸等の鉱酸で酸分解し、抽出工程をへ
てフリーのカルボン酸を得ることも出来る。The product can be used as a surfactant solution after pH adjustment, or can be acid-decomposed with a mineral acid such as hydrochloric acid and subjected to an extraction step to obtain a free carboxylic acid.
酸化反応は収率は90％以上に達する。The yield of the oxidation reaction reaches 90% or more.
以下に実施例を挙げて本発明をさらに詳細に説明する
が、本発明はこれらに限定されるものではない。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
比較例１ 特開昭53−141218号を追試するため５％パラジウムカー
ボン触媒を調製し、エチレンオキシド付加モル数５モル
［POE（５），以下POE（ｎ）でエチレンオキシド付加モ
ル数を表示する］のラウリルアルコールの酸化を行っ
た。Comparative Example 1 To test JP-A-53-141218, a 5% palladium carbon catalyst was prepared, and the number of moles of ethylene oxide added was 5 moles [POE (5), hereinafter POE (n) represents the number of moles of ethylene oxide added]. Oxidation of lauryl alcohol was performed.
酸素ガス導入口、ガス出口、温度計、サンプリング口、
攪拌器のついた１リッターフラスコにPOE（５）のラウ
リルアルコール（水酸基価:121）100g、イオン交換水40
0g、苛性ソーダ8.6g、先に調製した５％パラジウムカー
ボン触媒10g（含水率50％）を仕込んだ。攪拌下75℃ま
で昇温し、酸素ガス導入口より酸素ガスを常圧で系内に
バブリング導入した。５時間後反応速度は激減し、反応
は停止した。Oxygen gas inlet, gas outlet, thermometer, sampling port,
In a 1-liter flask equipped with a stirrer, POE (5) lauryl alcohol (hydroxyl value: 121) 100 g, deionized water 40
0 g, caustic soda 8.6 g, and 10 g of the previously prepared 5% palladium carbon catalyst (water content 50%) were charged. The temperature was raised to 75 ° C. with stirring, and oxygen gas was bubbled into the system through the oxygen gas inlet at normal pressure. After 5 hours, the reaction rate was drastically reduced and the reaction was stopped.
反応終了物は触媒分離後、塩酸分解し、クロロホルムで
抽出した。クロロホルムを減圧で除去し、反応混合物の
酸価と水酸基価から計算した収率は79モル％であった。After completion of the catalyst separation, the reaction product was decomposed with hydrochloric acid and extracted with chloroform. Chloroform was removed under reduced pressure, and the yield calculated from the acid value and the hydroxyl value of the reaction mixture was 79 mol%.
触媒調製法 ２％Te/10％Pd/C触媒 触媒第１成分および触媒第２成分がそれぞれパラジウ
ム、テルル、触媒担体が活性炭である本発明の触媒を調
製する。Catalyst Preparation Method 2% Te / 10% Pd / C Catalyst A catalyst of the present invention is prepared in which the catalyst first component and the catalyst second component are palladium and tellurium, and the catalyst carrier is activated carbon.
活性炭8.8gを100mlのイオン交換水に浸漬させておく。
一方、パラジウムおよびテルルの原料として塩化パラジ
ウムと酸化テルルを選ぶ。Immerse 8.8 g of activated carbon in 100 ml of deionized water.
On the other hand, palladium chloride and tellurium oxide are selected as raw materials for palladium and tellurium.
塩化パラジウム1.66gを18％の塩酸水溶液（conc HCl 14
ml＋イオン交換水20ml）34mlに溶解させる。また、酸化
テルル0.25gを18％の塩酸水溶液（conc HCl 24ml＋イオ
ン交換水40ml）64mlに溶解させる。Palladium chloride 1.66 g was added to 18% hydrochloric acid aqueous solution (conc HCl 14
ml + ion-exchanged water 20 ml) Dissolve in 34 ml. Also, 0.25 g of tellurium oxide is dissolved in 64 ml of 18% hydrochloric acid aqueous solution (conc HCl 24 ml + ion exchanged water 40 ml).
これらのパラジウムおよびテルルの塩酸水溶液を先に調
製した活性炭の水分散液中に添加し、攪拌下に常温で５
時間吸着処理を行う。The aqueous hydrochloric acid solution of palladium and tellurium was added to the previously prepared aqueous dispersion of activated carbon, and the mixture was stirred at room temperature for 5 hours.
Perform time adsorption processing.
次に、活性炭に吸着したパラジウム、テルルの還元処理
を行う為、加熱下、攪拌下に苛性ソーダ水溶液20g,37％
ホルマリン水溶液16mlを徐々に添加する。Next, to reduce the palladium and tellurium adsorbed on the activated carbon, heat and stir the caustic soda aqueous solution 20g, 37% under stirring.
16 ml of formalin aqueous solution is gradually added.
還元処理の終了後、冷却し触媒を濾別する。After completion of the reduction treatment, the mixture is cooled and the catalyst is filtered off.
得られた触媒は２％Te/10％Pd/C触媒であるが、含水率
は約50％である。触媒は乾燥することなく酸化反応に使
用することが出来る。The obtained catalyst is a 2% Te / 10% Pd / C catalyst, but the water content is about 50%. The catalyst can be used in the oxidation reaction without drying.
本発明の他の触媒もこれと同様の方法で調製することが
出来る。Other catalysts of the present invention can be prepared in a similar manner.
実施例１ 本発明の触媒として下表に示した４種を選んだ。触媒は
いずれもパラジウム（Pd）を触媒第１成分とし、テルル
（Te）、ビスマス（Bi）、スズ（Sn）、セレン（Se）を
触媒第２成分とする。触媒調製法は上記と全く同様に行
った。Example 1 Four catalysts shown in the table below were selected as the catalyst of the present invention. All the catalysts use palladium (Pd) as the catalyst first component, and tellurium (Te), bismuth (Bi), tin (Sn), and selenium (Se) as the catalyst second component. The catalyst preparation method was exactly the same as above.
これらの触媒を用い、比較例１で示したと同様の化合物
と反応条件で酸化反応を行った。Using these catalysts, an oxidation reaction was carried out under the same reaction conditions as the compound shown in Comparative Example 1.
反応結果を表−１にまとめた。The reaction results are summarized in Table-1.
表より収率も90モル％以上と高く、本発明の触媒の方が
比較例１に示した特開昭53−141218号で使用される５％
パラジウムカーボン触媒より優れていることが分かる。 The yield is higher than 90 mol% as shown in the table, and the catalyst of the present invention is 5% used in JP-A-53-141218 shown in Comparative Example 1.
It can be seen that it is superior to the palladium carbon catalyst.
実施例２ 実施例１の４％Bi/10％Pd/Cを用いて触媒再使用実験を
行った。Example 2 A catalyst reuse experiment was conducted using 4% Bi / 10% Pd / C of Example 1.
反応法に関しては反応時間を３時間にした以外は比較例
１と同様に行った。反応終了後は触媒を濾別し、再使用
を行った。但し、再使用の際は新触媒の補充は全く行っ
ていない。Regarding the reaction method, the same procedure as in Comparative Example 1 was carried out except that the reaction time was 3 hours. After completion of the reaction, the catalyst was filtered off and reused. However, no new catalyst was replenished at the time of reuse.
その結果、20回の再使用後でも触媒活性は全く衰えず、
平均収率として93％という値を得た。本実施例からも明
らかなように、本発明の触媒の耐久性は極めて優れたも
のであることが分かる。As a result, even after reuse 20 times, the catalytic activity does not deteriorate at all,
A value of 93% was obtained as an average yield. As is clear from this example, it is found that the catalyst of the present invention has extremely excellent durability.
実施例３ 実施例１の２の触媒を用いて、一般式(1)で表される種
々の化合物の酸化を行った。Example 3 Using the catalyst of Example 1-2, various compounds represented by the general formula (1) were oxidized.
RO(EO)nH (1) 反応条件等は比較例１に示すのと同様に行った。RO (EO) n H (1) Reaction conditions were the same as those shown in Comparative Example 1.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 51/235 Ｃ０８Ｇ 65/32 ＮＱＨ Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display area C07C 51/235 C08G 65/32 NQH
Claims (1)
鎖又は分岐のアルキル基を有するアルキルフェニル基、
又は炭素数８〜36の直鎖又は分岐のアルキル基、もしく
はアルケニル基を示し、ｎは１〜100の整数を示す） を水溶媒系で、反応温度30〜100℃、反応圧10気圧まで
の条件下、パラジウムを触媒第１成分とし、セレン、テ
ルル、スズおよびビスマスから成る群から選ばれる１種
以上を触媒第２成分として含有し、触媒第２成分と第１
成分の比率（第２成分／第１成分）が原子比で0.01〜2.
0であり、予め触媒第１成分と触媒第２成分とを担体に
担持させた担持触媒の存在下、反応系のpHを7.5以上に
調節しながら酸素もしくは酸素含有ガスで接触酸化する
ことを特徴とするカルボン酸塩の製造法。1. A compound represented by the general formula (1): RO (EO) n H (1) (wherein EO is ethylene oxide, R is an alkylphenyl having a linear or branched alkyl group having 4 to 14 carbon atoms). Base,
Or a linear or branched alkyl group having 8 to 36 carbon atoms, or an alkenyl group, and n is an integer of 1 to 100) in an aqueous solvent system at a reaction temperature of 30 to 100 ° C. and a reaction pressure of up to 10 atm. Under the conditions, palladium is used as the catalyst first component, and one or more kinds selected from the group consisting of selenium, tellurium, tin and bismuth is contained as the catalyst second component, and the catalyst second component and the first component are contained.
The ratio of the components (second component / first component) is 0.01 to 2.
It is 0, and is characterized by performing catalytic oxidation with oxygen or an oxygen-containing gas while adjusting the pH of the reaction system to 7.5 or higher in the presence of a supported catalyst in which a catalyst first component and a catalyst second component are previously supported on a carrier. And a method for producing a carboxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61041113A JPH075511B2 (en) | 1986-02-26 | 1986-02-26 | Method for producing carboxylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61041113A JPH075511B2 (en) | 1986-02-26 | 1986-02-26 | Method for producing carboxylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62198641A JPS62198641A (en) | 1987-09-02 |
| JPH075511B2 true JPH075511B2 (en) | 1995-01-25 |
Family
ID=12599410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61041113A Expired - Lifetime JPH075511B2 (en) | 1986-02-26 | 1986-02-26 | Method for producing carboxylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075511B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9233904B2 (en) | 2011-12-28 | 2016-01-12 | Kao Corporation | Method for producing polyoxyalkylene alkyl ether carboxylic acid or salt thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995032233A1 (en) * | 1994-05-24 | 1995-11-30 | Kao Corporation | Process for producing carboxylated polymer |
| US6110866A (en) * | 1998-12-09 | 2000-08-29 | Jay-Mar, Inc. | Surfactant coated products and methods for their use in promoting plant growth |
| JP5511369B2 (en) * | 2009-12-28 | 2014-06-04 | 花王株式会社 | Method for producing carboxylic acid |
| JP5520088B2 (en) * | 2010-03-10 | 2014-06-11 | 花王株式会社 | Method for producing ether carboxylate |
| JP5520089B2 (en) * | 2010-03-10 | 2014-06-11 | 花王株式会社 | Method for producing ether carboxylate |
| EP2719678B1 (en) | 2011-06-10 | 2015-11-18 | Kao Corporation | Method for manufacturing polyoxyethylene alkyl ether acetic acid |
| JP2013067565A (en) * | 2011-09-20 | 2013-04-18 | Kao Corp | Method of producing carboxylate |
| JP5801150B2 (en) * | 2011-09-20 | 2015-10-28 | 花王株式会社 | Method for producing carboxylate |
| WO2019116117A1 (en) * | 2017-12-13 | 2019-06-20 | Chevron Oronite Company Llc | Bimodal copolymer compositions useful as oil modifiers and lubricating oils comprising the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2851788A1 (en) * | 1978-11-30 | 1980-06-12 | Bayer Ag | METHOD FOR THE PRODUCTION OF ARYLOXIC ACID |
-
1986
- 1986-02-26 JP JP61041113A patent/JPH075511B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9233904B2 (en) | 2011-12-28 | 2016-01-12 | Kao Corporation | Method for producing polyoxyalkylene alkyl ether carboxylic acid or salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62198641A (en) | 1987-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH075511B2 (en) | Method for producing carboxylate | |
| JPH09505800A (en) | Method for alkylating estrone derivatives | |
| JP2001504428A (en) | Cerium and zirconium oxides, mixed oxides and solid solutions with improved thermal stability for exhaust gas catalysis and production method | |
| EP0015104A1 (en) | Preparation of biphenol by the oxidative coupling of alkylphenols | |
| JPH08511770A (en) | Oxime method | |
| JPH04221339A (en) | Production of (poly)oxyethylene alkyl ether acetic acid | |
| JPS61155356A (en) | Alkoxylated tertiary amine compound | |
| JPH0751541B2 (en) | Method for producing carboxylate | |
| IE58072B1 (en) | Process for the synthesis of 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoroisopropyl alcohol | |
| JP2540590B2 (en) | Method for producing aromatic carbonate compound | |
| JP3759328B2 (en) | Method for producing an aqueous solution of betaine | |
| CN1279012C (en) | Process for production of ruthenium (III) acetate solution | |
| JPS5945666B2 (en) | Method for producing aminocarboxylic acids | |
| JP3001862B2 (en) | Novel method for producing tetraalkyldiphenol | |
| US6589903B2 (en) | Method of synthesizing complexes of platinum and alkenylpolysiloxane, especially of platinum and divinyltetramethyldisiloxane | |
| JPH0546844B2 (en) | ||
| DE19962571A1 (en) | Production of trialkoxysilanes comprises reaction of silicon metal with an alcohol in the presence of a copper containing catalyst in an inert reaction medium comprising a diphenylalkane | |
| US6046356A (en) | Preparation of solutions of betaine | |
| US5237033A (en) | Preparation of polysilanes | |
| JP3417418B2 (en) | Method for producing alkylene carbonate | |
| JP7123002B2 (en) | Method for producing 1,6-hexanediol | |
| CN114075106B (en) | Preparation method of fatty alcohol ether carboxylic acid | |
| JPH0132825B2 (en) | ||
| EP1026146B1 (en) | A method for producing purified phenylenedioxydiacetic acids | |
| JPH0338537A (en) | Synthesis of biphenyl-4,4'-diol |