CN1507950A - Catalyst for oxyalkylation - Google Patents

Abstract

The present invention relates to a catalyst for alkoxylation reaction. Said catalyst has the following structure formula: [RO(CH2CH2O)nCH2COO]2-M, in which R is alkyl group or alkenyl of C2-C30, n=1-16, M is Ca or Mg, R is alkyl group or alkenyl of C6-C16 perfectly, n=1-9 is more ideal, and optimum M is Ca. Said catalyst has good compatibility with alkoxy compound, and its chemical property is more approaching to that of alkoxy compound, and it almost does not produce effect on application performance of product, at the same time it can ensure that the homologous compound in the obtained alkoxy compound must be made into narrow distribution, so that it can better overcome the defect of existent technology.

Description

A kind of catalyst for alkoxylation

Technical field

The present invention relates to a kind of catalyst for alkoxylation.

Background technology

Alkoxide compound is the important compound of a class, as alkoxide compound of the alkoxide compound of the alkoxide compound of alcohol, carboxylic acid, amine etc.Alkoxide compound can be used as non-ionic surface active agent mostly, in industries such as washing, textile printing and dyeing, agricultural chemicals, industry cleaning links, has a wide range of applications.In addition, it can also be as intermediate by other various anion surfactants of preparation such as sulfonation, phosphorylations.Alkoxide compound is conventionally by making by addition reaction under the existence of catalyst containing the compound of active hydrogen and oxirane or expoxy propane, the mixture that product is different polymerization degree.Industrial conventional catalyst is base catalyst at present, as KOH, NaOH and sodium methoxide etc.With strong alkali as a catalyst carry out that alkoxylation has that side reaction is few, by-products content is low, consersion unit is difficult for the advantages such as burn into reaction is easy to operate, with low cost.But shortcoming is that in product, unreacted free alcohol is more, homologue wider distribution in product, and require homologue in alkoxide compound product to be narrow distribution in many applications, some report also points out that the alkoxide compound of narrow distribution has its unique advantage.

Later research discovery, in alkoxylation product, homologue distributes and depends primarily on reaction catalyst used.For the object of the narrow distribution alkoxide compound of preparation, 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 catalyst; United States Patent (USP) 4,483,941 propose to use BF ₃with metal alkoxide compound as catalyst.Although use such catalyst to make distribution narrow, also brought other problem, as by-products content in product increases, and HF and BF ₃toxicity own is larger.What another problem deserving of attention was the catalyst that adopts due to alkoxylation with product is separated very difficult, general way is retained in product and in addition not separated, and this just requires the existence of catalyst the smaller the better on the serviceability impact of product.Although the alkoxylated polymerization product homologue wider distribution that traditional base catalyst makes, the compatibility of it and alkoxide compound is fine, but very little on the serviceability impact of product.It is poor with the compatibility of alkoxide compound that the existing alkoxylating catalyst that these can prepare narrow distribution alkoxide compound exists a total shortcoming, causes product appearance muddy.In addition these catalyst in chemical property with the differing greatly of alkoxide compound, how much this has also affected the serviceability of product.

Summary of the invention

The invention provides a kind of catalyst for alkoxylation, its technical problem to be solved is to make catalyst and alkoxide compound have better compatibility, and make great efforts to make the chemical property of catalyst also more approaching with alkoxide compound, reduce as far as possible the impact of catalyst on product serviceability, in the alkoxide compound product simultaneously obtaining, homologue must be narrow distribution.

Below the technical scheme that the present invention solves the problems of the technologies described above:

For a catalyst for alkoxylation, this catalyst has following structure:

[ROCH ₂CH ₂O _nCH ₂COO] ₂-M

Wherein:

R is C ₂～C ₃₀alkyl or alkenyl, n=1～16, M is Ca or Mg.

Above-mentioned R is C preferably ₆～C ₁₆alkyl or alkenyl, n=1～9 are even more ideal, M is preferably Ca.

Above-mentioned catalyst conventionally can be by the compound of calcic, as CaO, Ca (OH) ₂, or calcium carboxylates, as calcium formate, calcium acetate, calcium propionate, calcium butyrate and calcium metal etc., react and obtain with corresponding alcohol ether carboxylate.Reaction can be carried out in the solvent of the aqueous solution, organic solvent or both mixing, and organic solvent can be methyl alcohol, ethanol, isopropyl alcohol, butanols, amylalcohol or octanol etc.

This catalyst reaction is better active, and in the alkoxide compound product obtaining, homologue is narrow distribution.And because the chemical constitution of it and alkoxide compound is closely similar, all contain oxyalkylene addition unit, according to similar person's compatibility principle, catalyst is soluble in reaction system, can give full play to the reactivity of calcium ion.And this catalyst is nontoxic, to the following process of product and use, can not bring problem.This catalyst itself is a kind of polyfunctional surfactant, has the feature of anion surfactant, non-anion surfactant simultaneously, has good surface-active and good mildness and biological degradability.Therefore, compared with prior art, advantage of the present invention is that catalyst and alkoxide compound have better compatibility, its chemical property is also more approaching with alkoxide compound, serviceability to product exerts an influence hardly, in the alkoxide compound product that can guarantee to obtain, homologue must be narrow distribution simultaneously, has overcome preferably the defect that prior art exists.

Accompanying drawing explanation

Accompanying drawing is the content distribution figure of the different adduct number homologues of the alkoxide compound product for preparing of embodiment 2, comparative example 1 and comparative example 2.

The specific embodiment

One, the investigation of the preparation of catalyst and catalyst and alkoxide compound product compatibility

[embodiment 1～8]

200g alcohol ether carboxylate is joined in flask, and add 100g water and 100g isopropyl alcohol, be heated with stirring to 90 ℃, again calcium oxide or the magnesium oxide powder (acid number by alcohol ether carboxylate calculates) of equivalent mole are joined in flask gradually, fully after reaction, with rectificating method, water and solvent removal are made to catalyst.

By 600g C ₁₂～C ₁₄mixed alcohol and 20g catalyst join in the autoclave of 2 liters, rushing nitrogen replacement removes oxygen, be warming up to 100～120 ℃, vacuumize 0.5～1 hour, then be warming up to 160 ℃, the oxirane that passes into 30g carries out initiation reaction, after initiation reaction, is the oxirane (reacting required equivalent) of 380g constantly to adding total amount in reactor, and in reinforced process, keeping system pressure is 0.2～0.4MPa.Reaction finishes post curing 20 minutes, is cooled to 110 ℃ of left and right vacuumize degassing, finally obtains C ₁₂～C ₁₄mixed alcohol APEO.

The structural formula of the alcohol ether carboxylate raw material that each embodiment adopts and the catalyst of preparation is in Table 1, and the product appearance of alkoxylation is in Table 2.

Table 1.

	Alcohol ether carboxylate raw material	Catalyst
			Embodiment 1	??C 4H 9O-(CH 2CH 2O) 2-CH 2COOH	[C 1H 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 that alkoxide compound product homologue distributes

[comparative example 1]

Using the KOH of 3g as catalyst, join in reactor, all the other are identical with the preparation process of the alkoxide compound of embodiment 1～8.

[comparative example 2]

Using the sodium methoxide of 3g as catalyst, join in reactor, all the other are identical with the preparation process of the alkoxide compound of embodiment 1～8.

The content of the different adduct number homologues of liquid chromatography analysis for alkoxide compound product that embodiment 2, comparative example 1 and comparative example 2 are prepared, three's distribution situation is shown in shown in accompanying drawing, in the drawings, zero is embodiment 2; is comparative example 1; △ is comparative example 2.

Claims (4)

1, for a catalyst for alkoxylation, this catalyst has following structure:

[ROCH ₂CH ₂O _nCH ₂COO] ₂-M

Wherein:

R is C ₂～C ₃₀alkyl or alkenyl, n=1～16, M is Ca or Mg.

2, catalyst according to claim 1, is characterized in that R is C ₆～C ₁₆alkyl or alkenyl.

3, catalyst according to claim 1, is characterized in that n=1～9.

4,, according to the catalyst described in claim 1,2 or 3, it is characterized in that M is Ca.