JP4977609B2 - アルカリ土類をベースとするアルコキシル化触媒 - Google Patents
アルカリ土類をベースとするアルコキシル化触媒 Download PDFInfo
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- JP4977609B2 JP4977609B2 JP2007529827A JP2007529827A JP4977609B2 JP 4977609 B2 JP4977609 B2 JP 4977609B2 JP 2007529827 A JP2007529827 A JP 2007529827A JP 2007529827 A JP2007529827 A JP 2007529827A JP 4977609 B2 JP4977609 B2 JP 4977609B2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Fats And Perfumes (AREA)
Description
本発明は、アルカリ土類化合物を含んでなる混合物に強酸を添加することを包含する。このアルカリ土類化合物は、25℃で1リットル当たり少なくとも2グラムの水中の溶解度を有するイオン性アルカリ土類化合物であることが必要ではないが、好ましい。このように、塩化物、臭化物、ヨウ化物、硝酸塩、亜硝酸塩、リン酸塩、亜リン酸塩、硫酸塩、亜硫酸塩、カルボン酸塩、アルコキシド、フルオロホウ酸塩、フルオロケイ酸塩などが本発明の方法で使用可能なアルカリ土類金属のすべての好適な塩である。更には、触媒材料の形成において前出のアニオンを各々含んでなる2つ以上のアルカリ土類材料を含んでなる混合物の使用は、本発明の範囲内のものである。アルカリ土類金属塩はカルシウム塩であることが好ましく、この点において、酢酸カルシウムが特に好ましい。もう一つの態様においては、本発明の触媒が形成される混合物中に存在するマグネシウムの量は、存在するカルシウム化合物の全量基準で約0.1重量%と1.0重量%の間にある。すなわち、使用されるアルカリ土類化合物は、存在するカルシウムとマグネシウムの合わせた全重量基準で約0.1重量%と1.0重量%の間のマグネシウムを含有する酢酸カルシウムと酢酸マグネシウムの混合物である。
酸成分が水中で自由に解離した(100%イオン化)強酸であることが好ましいが、必要ではない。このような酸は化学者にはよく知られている。別に述べれば、本発明による触媒の製造における使用に好適な酸は、使用されるアルカリ土類化合物の原材料のアニオンの共役酸と同じように少なくとも強い酸強度(水中で測定した解離度)を有しなければならない。例えば、酢酸カルシウムと酢酸マグネシウムの混合物を原材料として使用する場合には、本発明による触媒の形成に使用される酸は、酢酸に対する酸解離定数よりも大きい酸解離定数を有しなければならない。
本発明により触媒を製造し得る組成物はカルボン酸を含有し得る。このカルボン酸が脂肪酸であるということは必要ではないが、好ましい。事実、直鎖、分岐、環状、芳香族、脂肪族、アルキルアリールであれ、約2と25個の間の炭素原子を有する任意のカルボン酸である。好適な酸は、1分子当たり単一の、2個の、3個以上のカルボン酸官能基を含有するものを含む。加えて、このカルボン酸成分は、1個、2個あるいは3個のオレフィン結合(二重結合、別名「不飽和結合」)を含有し得るか、あるいは飽和であり得る。特に好まれる酸はオレイン酸である。
本発明による触媒は、好ましくは、ポリアルキレングリコール;一方あるいは両方の末端にアルキル基を有し、末端のアルキル基が任意のC1−C25ヒドロカルビル基であるポリアルキレングリコール;ポリオキシアルキル化カルボン酸;または室温で液体である、C1−C6アルキレンオキシドの本質的に任意のポリマー(ブロックあるいはランダム)などのポリエーテル材料であるエーテル成分を含み得る。一つの好まれる態様においては、エーテル成分は約100と1500の間の分子量を有する。もう一つの態様においては、エーテル成分は約100と1000の間の分子量を有する。この明細書内には、約100と1000の間の分子量を有するポリアルキレングリコールと、100と1000の間の分子量を有するC1−C10アルキルでキャップされたポリアルキレングリコールが含まれる。前出のいずれかを含む任意の混合物が本発明での使用に好適である。
90グラムのPRIOLENE(登録商標)6933のオレイン酸および48グラムの酢酸カルシウム一水和物を500mlのビーカー中で合体することにより、アルコキシル化触媒を製造した。上述のSilversonミキサーを用いて、酢酸カルシウムを分散した。これに12グラムの濃硫酸を撹拌しながら約1分間にわたってゆっくりと添加した。この混合物は初めは黒色に転じ、混合時に黄色となる。引き続いて、Silverson混合物を用いて、この混合物を均質となるまで分散した。この反応混合物を冷却し、そして更なる量の50グラムのPrioleneを添加して、30%の活性触媒を含有する低粘度の分散物を得た。
と図示され得る。(この明細書および添付のクレームの範囲で使用されるように、語「ヒドロカルビル」は、置換基または基を指す場合には、当分野の熟練者にはよく知られている通常の意味で使用される。特に、これは、分子の残りに直接に結合した炭素原子を有し、そして主として炭化水素の性格を有する基を指す。ヒドロカルビル置換基あるいは基の例は、(1)炭化水素置換基、すなわち脂肪族(例えば、アルキルまたはアルケニル)、脂環式(例えば、シクロアルキル、シクロアルケニル)置換基および芳香族−、脂肪族−および脂環式置換芳香族置換基、ならびに環が分子の別の部分を通って完結する環状置換基(例えば、2個の置換基が一緒になって脂環式基を形成する);(2)置換炭化水素置換基、すなわち、本発明の文脈で、大部分炭化水素の置換基を変えない非炭化水素基を含有する置換基(例えば、ハロ(特にクロロおよびフルオロ)、ヒドロキシ、アルコキシ、メルカプト、アルキルメルカプト、ニトロ、ニトロソおよびスルホキシ);(3)ヘテロ置換基、すなわち、大部分炭化水素の性格を有する一方で、本発明の文脈において、環または鎖中に、そうでなければ炭素原子から構成される炭素以外を含有する置換基を含む。ヘテロ原子はイオウ、酸素、窒素を含み、そしてピリジン、フリル、チエニルおよびイミダゾリルなどの置換基を網羅する。一般に、たかだか2個の、好ましくはたかだか1個の非炭化水素置換基がヒドロカルビル基中で10個の炭素原子ごとに存在する;通常、ヒドロカルビル基中には非炭化水素置換基は存在しない。)上記の反応は、R1基がカルボニル炭素に関してアルコキシレート部分の遠位末端に結合しているように書かれているが、この開示は、また、R1基がカルボニル炭素に関してアルコキシレート部分の近位末端に結合している態様も開示している。本発明は、限定するのではないが、エチレンオキシドとプロピレンオキシドの混合物を使用して、混合アルコキシ部分のランダム分布を生成することを含んで、単一種以上のアルキレンオキシドがアルコキシル化剤として使用される場合を更に含む。加えて、本発明は、例えば最初にある量の一つのアルキレンオキシドを反応させ、引き続いて異なるアルキレンオキシドを反応させることなど、アルキレンオキシドをブロック付加させることを含む。
Claims (9)
- カルボン酸、アルコールおよびエステルを1つ以上のアルキレンオキシドによりアルコキシル化するのを促進するのに有用な触媒を形成する方法であって、
a)アルカリ土類化合物を、カルボン酸;100と1000の間の分子量を有するポリアルキレングリコール;100と1000の間の分子量を有するC1−C10アルキルでキャ
ップされたポリアルキレングリコール;および前出のいずれかを含む混合物からなる群から選択される1つ以上の更なる材料と合体させて第1の混合物を形成させ;
b)硫酸、有機スルホン酸、有機スルホン酸塩、硫酸塩、重硫酸塩、亜硫酸塩、重亜硫酸塩、任意のC1〜C12カルボン酸または任意のC1〜C12カルボン酸塩からなる群から選択される少なくとも1つのイオン性化学種を前記第1の混合物と合体して第2の混合物を形成し;そして
c)前記第2の混合物を均一な外観に混合して完成した触媒を提供する、
段階を含んでなる方法。 - 前記アルカリ土類化合物がカルシウム化合物である請求項1に記載の方法。
- 前記カルシウム化合物が酢酸カルシウムである請求項2に記載の方法。
- 前記アルカリ土類化合物をカルボン酸と合体させる請求項1〜3のいずれか1項に記載の方法。
- 前記第1の混合物を硫酸と合体させる請求項1〜4のいずれか1項に記載の方法。
- R1が水素又はメチルである請求項6に記載のアルコキシル化方法。
- R2がC12−C18ヒドロカルビル基である請求項6又は7に記載のアルコキシル化方法
。 - R3がメチル又はエチルである請求項6〜8のいずれか1項に記載のアルコキシル化方
法。
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PCT/US2005/019050 WO2006025898A1 (en) | 2004-08-26 | 2005-05-31 | Alkaline earth-based alkoxylation catalysts |
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EP2349974A1 (en) * | 2008-10-29 | 2011-08-03 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of acylated secondary alcohol alkoxylates and secondary alcohol alkoxylates |
US9056828B2 (en) | 2010-09-02 | 2015-06-16 | Kolb Distribution Ltd. | Alkoxylation method of fatty acid alkyl esters |
CN103124764B (zh) | 2010-09-30 | 2014-12-24 | 亨斯迈石油化学有限责任公司 | 衍生自基于生物柴油的烷基化芳族化合物的表面活性剂 |
BR112013009971A2 (pt) * | 2010-10-25 | 2016-08-02 | Stepan Co | composição de éster graxo alcoxilado, derivado feito por sulfonação ou sulfitação da composição, emulsificante aniônico e não aniônico para composições agrícolas, solvente agrícola. composição de herbicida solúvel em água, composição antimicrobiana, limpador de superfície áspera aquoso, sabonete e detergente para vestuário sujo |
SG11201406438WA (en) * | 2012-04-13 | 2014-12-30 | Lion Corp | Alkoxylation catalyst, method for producing catalyst, and method for producing fatty acid alkyl ester alkoxylate using catalyst |
MY188147A (en) * | 2014-04-24 | 2021-11-24 | Lion Corp | Method for producing fatty acid alkyl ester alkoxylate |
CN105498842B (zh) * | 2014-09-25 | 2018-06-08 | 中国石油化工股份有限公司 | 脂肪酸甲酯乙氧基化催化剂及其应用 |
JP6403325B2 (ja) * | 2014-12-26 | 2018-10-10 | ライオン株式会社 | 脂肪酸アルキルエステルアルコキシレートの製造方法 |
US10315189B2 (en) | 2015-09-04 | 2019-06-11 | Lion Corporation | Ethoxylation catalyst and manufacturing method therefor |
CN107442173B (zh) * | 2016-05-30 | 2020-10-16 | 中国石油化工股份有限公司 | 脂肪酸甲酯乙氧基化催化剂 |
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EP0085167A1 (en) * | 1981-12-24 | 1983-08-10 | Conoco Phillips Company | Alkoxylation with calcium and magnesium salts |
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US7629487B2 (en) | 2009-12-08 |
CN101374599B (zh) | 2013-01-09 |
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