CN1215029C - Method for preparing alkoxy compound by oxyalkylation - Google Patents
Method for preparing alkoxy compound by oxyalkylation Download PDFInfo
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- CN1215029C CN1215029C CN 02155059 CN02155059A CN1215029C CN 1215029 C CN1215029 C CN 1215029C CN 02155059 CN02155059 CN 02155059 CN 02155059 A CN02155059 A CN 02155059A CN 1215029 C CN1215029 C CN 1215029C
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- alkoxy compound
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- active hydrogen
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Abstract
The present invention relates to a method for preparing an alkoxy compound by an oxyalkylation reaction in the presence of a catalyst, which comprises: a compound containing active hydrogen and propylene oxide are used as raw materials, reaction temperature is from 100 to 220 DEG C, and reaction pressure is from 0.1 to 0.6MPa. The catalyst has the following structure of [RO-(-CH2CH2O)-nCH2COO]2-M, wherein R is C2 to C30 alkyl or alkenyl, n is from 1 to 16, and M is Ca or Mg. The consumption of the catalyst is determined according to the weight ratio of 100:0.3 to 8 of the compound containing active hydrogen to the catalyst. The present invention has the advantages that the adopted catalyst and the alkoxyl compound have better compatibility, the chemical properties of the catalyst are close to that of the alkoxyl compound, no influence is produced on the service performance of the product, homologous compounds in the obtained alkoxyl compound product can be guaranteed to be in narrow distribution, and the defects of the prior art are favorably overcome.
Description
Technical field
The present invention relates to the method that alkoxylation prepares alkoxy compound.
Background technology
Alkoxy compound is the important compound of a class, as the alkoxy compound of alcohol, the alkoxy compound of carboxylic acid, the alkoxy compound of amine etc.Alkoxy compound can be used as nonionogenic tenside mostly, has a wide range of applications in industries such as washing, textile printing and dyeing, agricultural chemicals, industry cleanings.In addition, it can also be as intermediate by other various anion surfactants of preparation such as sulfonation, phosphorylations.Alkoxy compound can be made by addition reaction in the presence of catalyzer by compound that contains reactive hydrogen and propylene oxide usually, and product is the mixture of different polymerization degree.Industrial catalyzer commonly used is a basic catalyst at present, as KOH, NaOH and sodium methylate etc.With highly basic as catalyzer carry out that alkoxylation has that side reaction is few, by-products content is low, conversion unit is difficult for advantages such as the burn into reaction is easy to operate, with low cost.But shortcoming is that the unreacted free alcohol is more in the product, homologue wider distribution in the product, and homologue is narrow distribution in many Application Areass requirement alkoxy compound products, some report points out that also the alkoxy compound of narrow distribution has its unique advantage.
Later discovers, homologue distributes and depends primarily on the used catalyzer of reaction in the alkoxylation product.For the purpose of the narrow distribution alkoxy compound of preparation, an acidic catalyst is used in some patent suggestion, and as United States Patent (USP) 4,456,697 propose to use HF and metal alkoxide compound as catalyzer; United States Patent (USP) 4,483,941 propose to use BF
3With the metal alkoxide compound as catalyzer.Though use such catalyzer to make distribution narrow, also brought other problem, increase as by-products content in the product, and HF and BF
3Toxicity own is bigger.Another problem deserving of attention is because the catalyzer that alkoxylation adopts is very difficult with separating of product, general way is it is retained in the product and is not separated, and this just requires the existence of catalyzer the smaller the better to the use properties influence of product.Though the alkoxylated polymerization product homologue wider distribution that traditional basic catalyst makes, the consistency of it and alkoxy compound is fine, and is but very little to the use properties influence of product.It is relatively poor with the consistency of alkoxy compound that there is a total shortcoming in the existing alkoxylating catalyst that these can prepare narrow distribution alkoxy compound, causes the product appearance muddiness.In addition these catalyzer on chemical property with the differing greatly of alkoxy compound, how much this has also influenced the use properties of product.
Summary of the invention
The invention provides a kind of method for preparing alkoxy compound by alkoxylation, its technical problem to be solved is to use in the catalyzer of alkoxylation and alkoxy compound better consistency, and make great efforts to make the chemical property of catalyzer also more approaching with alkoxy compound, reduce the influence of catalyzer to the product use properties as far as possible, homologue must be narrow distribution in the alkoxy compound product that obtains simultaneously.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of method that in the presence of catalyzer, prepares alkoxy compound by alkoxylation, this method is a raw material with active hydrogen compounds and propylene oxide, temperature of reaction is 90～200 ℃, and reaction pressure is 0.1～0.5MPa, and catalyzer has following structure:
Wherein:
R is C
2～C
30Alkyl or alkenyl, n=1～16, M is Ca or Mg.
Catalyst consumption is weight ratio=100: 0.3～8 of active hydrogen compounds and catalyzer, be preferably 100: 0.5～and 5.R in the catalyzer is C preferably
6～C
16Alkyl or alkenyl, n=1～9 are even more ideal, M is preferably Ca.
Above-mentioned active hydrogen compounds mainly comprises:
The alcohol that contains 1～30 carbon atom and 0～3 two key is as methyl alcohol, ethanol, propyl carbinol, hexanol, octanol, decyl alcohol, dodecanol, tetradecanol, cetyl alcohol, 9--hexadecenol, Stearyl alcohol, oleyl alcohol, 22 carbon alcohol etc.Comparatively suitable is the straight-chain fatty alcohol that contains 8～18 carbon atoms.These alcohol can use separately, also can mix use, as industrial frequent use, can be the mixed fatty alcohol that contains even carbon that the fatty acid methyl ester hydrogenation by animal or plant obtains, also can be the mixed fatty alcohol that contains odd number carbon that obtains by carbonyl process.
The lipid acid that contains the two keys of 1～36 carbon atom and 0～3 is as formic acid, acetate, propionic acid, butyric acid, caproic acid, sad, capric acid, lauric acid, tetradecanoic acid, palmitinic acid, oleic acid, linolic acid, stearic acid etc.These lipid acid also can be natural or the synthetic mixture use.
Contain 1～24 carbon atom one, two, trialkyl phenol, as octyl phenol, nonyl phenol etc.
Molecular weight is 200～2000 polyoxyethylene glycol or polypropylene glycol.
Alkyl is the uncle or the secondary amine of 1～24 carbon atom.
Some polyol compounds also belong to this type of active hydrogen compounds, comprise the derivative of glycerine or glycerine, and carbohydrate and carbohydrate derivative, as the derivative of glucose, Sorbitol Powder, alkylglycoside or these materials.
Above-mentioned catalyzer usually can be by calcareous compound, as CaO, Ca (OH)
2, or calcium carboxylates, as calcium formiate, lime acetate, calcium propionate, Calcium Butyrate and calcium metal etc., obtain with corresponding alcohol ether carboxylate reaction.Reaction can be carried out in the aqueous solution, organic solvent or both blended solvents, and organic solvent can be methyl alcohol, ethanol, Virahol, butanols, amylalcohol or octanol etc.
Essence of the present invention is to have adopted a kind of new alkoxylation catalyzer, and other processing condition of reaction are identical as temperature of reaction, reaction pressure and prior art, and the alkoxylation raw material that catalyzer uses does not have difference with prior art yet.This catalyzer all contains oxyalkylene addition unit owing to closely similar with the chemical structure of alkoxy compound, and according to similar person's compatibility principle, this catalyzer is soluble in the reaction system, can give full play to the reactive behavior of calcium ion.And this catalyzer is nontoxic, can not bring problem to the following process of product with using.On the other hand, this catalyst themselves is a kind of multifunctional meter surface-active agent, has the feature of anion surfactant, non-anion surfactant simultaneously, has active and good mildness and the biological degradability of surface of good.Therefore, compared with prior art, advantage of the present invention is that the catalyzer and the alkoxy compound that adopt have better consistency, its chemical property is also more approaching with alkoxy compound, use properties to product exerts an influence hardly, homologue must be narrow distribution in the alkoxy compound product that can guarantee to obtain simultaneously, has overcome the defective that prior art exists preferably.
Description of drawings
Accompanying drawing is the content distribution figure of the different adduct number homologues of the alkoxy compound product for preparing of embodiment 2, comparative example 1 and comparative example 2.
Embodiment
Below will further prove positively effect of the present invention by embodiment, as preceding described, essence of the present invention is to have adopted a kind of new alkoxylation catalyzer, other processing condition of reaction, identical as temperature of reaction, reaction pressure and prior art, the alkoxylation raw material that catalyzer uses does not have difference with prior art yet.Therefore embodiment pays attention to the description to the catalyzer that adopts, and other processing parameter of reaction, the various active hydrogen compounds raw materials of employing are not enumerated respectively one by one.
One, the investigation of Preparation of catalysts and catalyzer and alkoxy compound product consistency
[embodiment 1～8]
The 200g alcohol ether carboxylate is joined in the flask, and adding 100g water and 100g Virahol, be heated with stirring to 90 ℃, calcium oxide or magnesium oxide powder (acid number by alcohol ether carboxylate calculates) with the equivalent mole joins in the flask gradually again, and fully the reaction back promptly makes catalyzer to water and solvent removal with rectificating method.
With 600g C
12～C
14Alcohol mixture and 20g catalyzer join in 2 liters the autoclave, towards nitrogen replacement oxygen is removed, be warming up to 100～120 ℃, vacuumized 0.5～1 hour, be warming up to 160 ℃ then, the propylene oxide that feeds 30g carries out initiation reaction, and adding total amount constantly in reactor after the initiation reaction is the propylene oxide (reacting required equivalent) of 380g, and keeping system pressure in the reinforced process is 0.2～0.4MPa.Reaction finishes post curing 20 minutes, is cooled to 110 ℃ of left and right sides vacuumize degassing, finally obtains C
12～C
14The alcohol mixture Soxylat A 25-7.
The structural formula of the alcohol ether carboxylate raw material that each embodiment adopts and the catalyzer of preparation sees Table 1, and the product appearance of alkoxylation sees Table 2.
Table 1.
| The alcohol ether carboxylate raw material | Catalyzer | |
| Embodiment 1 | C 4H 9O-(CH 2CH 2O) 2-CH 2COOH | [C 4H 9O-(CH 2CH 2O) 2-CH 2COO] 2-Ca |
| Embodiment 2 | C 12H 25O-(CH 2CH 2O) 5-CH 2COOH | [C 12H 25O-(CH 2CH 2O) 5-CH 2COO] 2-Ca |
| Embodiment 3 | C 4H 9O-(CH 2CH 2O) 5-CH 2COOH | [C 4H 9O-(CH 2CH 2O) 5-CH 2COO] 2-Mg |
| Embodiment 4 | C 8H 17O-(CH 2CH 2O) 3-CH 2COOH | [C 8H 17O-(CH 2CH 2O) 3-CH 2COO] 2-Mg |
| Embodiment 5 | C 12H 25O-(CH 2CH 2O) 9-CH 2COOH | [C 12H 25O-(CH 2CH 2O) 9-CH 2COO] 2-Ca |
| Embodiment 6 | C 8H 17O-(CH 2CH 2O) 7-CH 2COOH | [C 8H 17O-(CH 2CH 2O) 7-CH 2COO] 2-Ca |
| Embodiment 7 | C 16H 33O-(CH 2CH 2O) 7-CH 2COOH | [C 16H 33O-(CH 2CH 2O)7-CH 2COO] 2-Mg |
| Embodiment 8 | C 12H 25O-(CH 2CH 2O) 6-CH 2COOH | [C 12H 25O-(CH 2CH 2O) 6-CH 2COO] 2-Mg |
Table 2.
| Product appearance | |
| Embodiment 1 | Limpid |
| Embodiment 2 | Limpid |
| Embodiment 3 | Limpid |
| Embodiment 4 | Limpid |
| Embodiment 5 | Limpid |
| Embodiment 6 | Limpid |
| Embodiment 7 | Limpid |
| Embodiment 8 | Limpid |
Two, the investigation of alkoxy compound product homologue distribution
[comparative example 1]
The KOH of 3g is joined in the reactor as catalyzer, and all the other are identical with the preparation process of the alkoxy compound of embodiment 1～8.
[comparative example 2]
The sodium methylate of 3g is joined in the reactor as catalyzer, and all the other are identical with the preparation process of the alkoxy compound of embodiment 1～8.
The alkoxy compound product that embodiment 2, comparative example 1 and comparative example 2 are prepared is with the content of the different adduct number homologues of liquid chromatography analysis, and three's distribution situation sees shown in the accompanying drawing that in the drawings, zero is embodiment 2; is a comparative example 1; △ is a comparative example 2.
Claims (10)
1, a kind of method that in the presence of catalyzer, prepares alkoxy compound by alkoxylation, this method is a raw material with active hydrogen compounds and propylene oxide, temperature of reaction is 90～200 ℃, and reaction pressure is 0.1～0.5MPa, and catalyzer has following structure:
Wherein:
R is C
2～C
30Alkyl or alkenyl, n=1～16, M is Ca or Mg,
Catalyst consumption is weight ratio=100: 0.3～8 of active hydrogen compounds and catalyzer.
2, the method for preparing alkoxy compound according to claim 1 is characterized in that described catalyst consumption is weight ratio=100: 0.5～5 of active hydrogen compounds and catalyzer.
3, the method for preparing alkoxy compound according to claim 1 is characterized in that R is C in the described catalyzer
6～C
16Alkyl or alkenyl.
4, the method for preparing alkoxy compound according to claim 1 is characterized in that n=1 in the described catalyzer～9.
5, according to claim 1,2, the 3 or 4 described methods that prepare alkoxy compound, it is characterized in that M is Ca in the described catalyzer.
6, the method for preparing alkoxy compound according to claim 1 is characterized in that described active hydrogen compounds is the alcohol that contains 1～30 carbon atom and 0～3 two key.
7, the method for preparing alkoxy compound according to claim 1 is characterized in that described active hydrogen compounds is the lipid acid that contains 1～36 carbon atom and 0～3 two key.
8, the method for preparing alkoxy compound according to claim 1, it is characterized in that described active hydrogen compounds be contain 1～24 carbon atom one, two, trialkyl phenol.
9, the method for preparing alkoxy compound according to claim 1 is characterized in that described active hydrogen compounds is that molecular weight is 200～2000 polyoxyethylene glycol or polypropylene glycol.
10, the method for preparing alkoxy compound according to claim 1 is characterized in that described active hydrogen compounds is that alkyl is the primary amine or the secondary amine of 1～24 carbon atom.
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|---|---|---|---|
| CN 02155059 CN1215029C (en) | 2002-12-19 | 2002-12-19 | Method for preparing alkoxy compound by oxyalkylation |
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| CN 02155059 CN1215029C (en) | 2002-12-19 | 2002-12-19 | Method for preparing alkoxy compound by oxyalkylation |
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| CN100357248C (en) * | 2004-12-17 | 2007-12-26 | 辽宁奥克化学集团有限公司 | Fatty acid ester alkoxylating method and dedicated equipment therefor |
| CN106423285B (en) * | 2015-08-12 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of fatty acid methyl ester ethoxylation catalyst |
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