CN106423270A - Synthesis method of fatty acid methyl ester ethoxylation catalyst - Google Patents
Synthesis method of fatty acid methyl ester ethoxylation catalyst Download PDFInfo
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Abstract
The invention relates to a synthesis method of a fatty acid methyl ester ethoxylation catalyst in order to solve the problem of low EO distribution index in a reaction product of catalysts in the prior art. The method comprises the following steps: 1, mixing cyclodextrin with C1-C4 alcohol according to a mass ratio of 1:(1-10) to obtain a mixture i; 2, adding alkali earth metal salt and group VIII metal salt to the mixture i in order to obtain a mixture ii, wherein a mass ratio of the alkali earth alkali metal to the group VIII metal salt to the mixture i is (0.1-0.3):(0.01-0.10):1; 3, adjusting the pH value of the mixture ii to 5-8 in order to obtain a mixture iii; and 4, carrying out vacuum drying on the mixture iii at 100 DEG C or less in order to obtain the catalyst. The method well solves the technical problem, and can be used in the fatty acid methyl ester ethoxylation reaction.
Description
Technical field
The present invention relates to a kind of synthetic method for fatty acid methyl ester ethoxylation catalyst.
Background technology
Fatty acid methyl ester ethoxy compound (ethoxylated fatty acid methyl esters), abbreviation FMEE, is a kind of new
The ester-ether type nonionic surfactant of double end-blockings.Due to fatty acid methyl ester ethoxy compound one end have similar to oils and fatss
- OCH3, according to the principle of similar compatibility, compared with traditional fatty acid polyether, aliphatic alcohol polyether etc., has higher dirt-removing power,
There is good water solubility, fusing point is low, emulsion dispersion ability is strong, the advantages of foam is few；In addition this product is degradable, is a kind of real
Environment-friendly type surfactant.Fatty acid methyl ester compound be widely applied to leather, weaving, in cosmetic industry.FMEE exists
Close to TX, NP and OP containing APEO series in various performances, under the background abroad environmental protection being strict with, use
The toy of FMEE replacement TX or NP process, floor, textile garment etc., it is possible to reduce the trade dispute leading in exit procedure.
Due to fatty acid methyl ester unlike fatty acid, fatty alcohol or fatty amine etc. contain active hydrogen, therefore it is difficult to traditional acid base catalysator
Ethoxylation (ethyleneoxide addition, i.e. EO addition), that is, enable, conversion ratio is also low, and product impurity content is high, at present mostly
Using bimetallic or poly-metal deoxide or salt as catalyst.Reaction temperature is 160～180 DEG C, and reaction pressure is left in 0.3MPa
The right side, catalyst amount 0.1～1.0%
United States Patent (USP) US6008392 (Process for Preparing Alkoxylated Fatty Acid Alkyl Esters) discloses one
Plant fatty acid methyl ester ethoxylation catalyst, catalyst, mainly based on Al/Mg brucite, adds a small amount of LiOH or SnO simultaneously2
Constitute.For methyl laurate ethoxylation, find and do not add LiOH or SnO2When, unreacted EO content more than 1.5%,
[EO adduction number accounts for, in the component of n ± 2 scope, content (the wherein n (not including raw alcohol and PEG) in total component to EO profile exponent
EO adduction number for major constituent)], less than 70%；Add LiOH or SnO2Preferably, but catalyst amount is all more than 1.0%,
Response speed is slow.
United States Patent (USP) US5220246 (Process for Alkoxylation of Esters and Products Produced Therefrom)
Disclose a kind of activity alkoxide calcium aluminum composite catalyst and be used for coconut acid methylester ethoxylation, the average adduct number of EO is 8, product
Middle Polyethylene Glycol is higher than 2.0%, and unreacted fatty acid methyl ester is more than 0.5%, and catalyst amount is 1.0%.
The weak point of the catalyst of above-mentioned prior art is：In product, EO profile exponent is low, by-product is many.
Content of the invention
After one of the technical problem to be solved is catalyst ethoxylation present in prior art, ethoxylation is produced
In product, EO profile exponent is low, the problem more than by-product, provides a kind of synthetic method of new fatty acid methyl ester ethoxylation catalyst,
The method has the catalyst obtaining for EO narrowly distributing, by-product in ethoxylated products during fatty acid methyl ester ethoxylation
Few feature.
The two of the technical problem to be solved are the catalyst that the described synthetic method of one of above-mentioned technical problem obtains.
The three of the technical problem to be solved are the catalyst described in two of above-mentioned technical problem in fatty acid methyl ester ethoxylation
In application.
For solving one of above-mentioned technical problem, technical scheme is as follows：The synthesis side of fatty acid methyl ester ethoxylation catalyst
Method, including following preparation process：
(1) by mass ratio be 1:(1～10) cyclodextrin and C1～C4Alcohol be mixed to get mixture i；For ease of mixing, can pass through
The mode of heating reduces the viscosity of cyclodextrin；
(2) alkali salt and VIII race's slaine are added in mixture i and are mixed to get mixture ii, wherein alkali salt,
VIII race's slaine and mixture i mass ratio are (0.1～0.3):(0.01～0.10):1；
(3) pH to 5～8 with adjusting mixture ii obtains mixture iii；
(4) mixture iii is vacuum dried below 100 DEG C and obtains described catalyst.
For accelerating the mixing velocity of above-mentioned steps (1) and/or step (2), mix preferably under heating state.Above-mentioned technical side
In case, when step (3) adjusts the pH of mixture ii, it is preferred to use concentrated sulphuric acid, concentration is most preferably adopted to adjust for pH for 98wt%
Section agent.
In technique scheme, it is as follows that described cyclodextrin structure leads to formula (I)：
Wherein Z1、Z2、Z3Selected from H ,-CH3、-CH2-CHOH-CH3Base, preferably-CH3；N is selected from 6～12 integer,
Preferably 6～8 integer, more preferably 7.In place of being related to cyclodextrin in the embodiment of the present invention and comparative example, n is 7.
In technique scheme, described alcohol can be monohydric alcohol.As an example, described alcohol can be selected from methanol, ethanol, just
Propanol, isopropanol, n-butyl alcohol, 2- butanol, 2- methyl isophthalic acid-propanol or 2- methyl-2-propanol.
In technique scheme, described alcohol is C2～C4Dihydroxylic alcohols.As an example, described alcohol can selected from ethylene glycol, 1,2-
Propylene glycol, 1,3-PD.
In technique scheme, described alkali salt and VIII race's slaine preferably independently are selected from nitrate, acetate or hydrochlorate, more
Preferably acetate.
In technique scheme, described alkaline-earth metal preferably is selected from least one in magnesium, calcium, strontium and barium.Described alkaline-earth metal
Include simultaneously when magnesium and barium than independent include magnesium and do not include barium effect good, also than independent include barium and do not include magnesium effect good.
In technique scheme, described VIII race's slaine preferably is selected from ferrum, cobalt, at least one in nickel.Described VIII race's metal wraps simultaneously
Include when ferrum and nickel than independent include ferrum and do not include nickel effect good, also than independent include nickel and do not include ferrum effect good.
As the most preferred technical scheme：Described cyclodextrin is 2,3,6- TM-β-CD (i.e. Z1、Z2、Z3For-CH3)；
Described alkaline-earth metal includes magnesium and barium simultaneously, and described VIII race's metal includes ferrum and nickel simultaneously.
In technique scheme, step (1) cyclodextrin and C1～C4Alcohol mass ratio be preferably 1:(2.5～5).In step (3)
The preferred pH of pH value be more than or equal to 5 and be less than 7, more preferably pH be 5.5～6.5.In step (1) described in step (2)
Heating-up temperature is preferably 60～120 DEG C；Heat time heating time is preferably 10～60min.Described in step (4), vacuum drying temperature is excellent
Elect 50 DEG C as less than 100 DEG C, the time being dried is preferably 10～60min.
For solving the two of above-mentioned technical problem, technical scheme is as follows：Any one technical scheme of one of above-mentioned technical problem
The catalyst that described synthetic method obtains.
For solving the three of above-mentioned technical problem, technical scheme is as follows：Described in the two of above-mentioned technical problem, catalyst is in fat
Application in sour methyl ester ethoxylation.
The catalyst of the present invention is all evaluated according to following process：By 100～300g fatty acid methyl ester and catalyst (for fatty acid
0.1～0.8wt% of methyl ester) add in 1 liter of rustless steel autoclave with stirring slurry, it is warming up to 80 DEG C under stirring, evacuation
10min, removing moisture and low-boiling point material；Then with nitrogen displacement at least 3 times；150～180 DEG C of temperature and pressure 0.3～
Under 0.6MPa, continuous Deca oxirane (EO) is to required amount；After aging 30min, logical cooling water is cooled down,
Release, removes product, weighs, analyzes.
Evaluation result shows, the fatty acid methyl ester ethoxylated products EO profile exponent of catalyst of the present invention is more than 80%, total by-product
Product (Polyethylene Glycol or polypropylene glycol, unreacted fatty acid methyl ester) are less than 1.0wt%, and catalyst amount (accounts for less than 1.0wt%
Output aggregate quality).The catalyst that therefore present invention provides has the characteristics that ethoxylated products EO profile exponent height, side-product are few.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 2g Glacial acetic acid magnesium, 0.5g Glacial acetic acid ferrum and 100g mixture i in band returned cold
In solidifying there-necked flask, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；The sulphuric acid being 98wt% with concentration is strong
It is added drop-wise in mixture ii under strong stirring, make mixture pH be 6.0, after cooling, obtain mixture iii；By mixture iii at 80 DEG C
Under, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 2】
By 40g2,3,6- TM-β-CD and 160 isopropanols in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 2g Glacial acetic acid magnesium, 0.5g Glacial acetic acid nickel and 100g mixture i in band returned cold
In solidifying there-necked flask, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；The sulphuric acid being 98wt% with concentration is strong
It is added drop-wise in mixture ii under strong stirring, make mixture pH be 6.0, after cooling, obtain mixture iii；By mixture iii at 80 DEG C
Under, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 3】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 2g Glacial acetic acid barium, 0.5g Glacial acetic acid ferrum and 100g mixture i in band returned cold
In solidifying there-necked flask, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；The sulphuric acid being 98wt% with concentration is strong
It is added drop-wise in mixture ii under strong stirring, make mixture pH be 6.0, after cooling, obtain mixture iii；By mixture iii at 80 DEG C
Under, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 4】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 2g Glacial acetic acid magnesium, 0.5g Glacial acetic acid nickel and 100g mixture i in band returned cold
In solidifying there-necked flask, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；The sulphuric acid being 98wt% with concentration is strong
It is added drop-wise in mixture ii under strong stirring, make mixture pH be 6.0, after cooling, obtain mixture iii；By mixture iii at 80 DEG C
Under, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 5】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium, 0.5g Glacial acetic acid ferrum and 100g are mixed
Compound i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；With concentration it is
The sulphuric acid of 98wt% is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, obtains mixture iii after cooling；
By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 6】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium and 0.5g Glacial acetic acid nickel and 100g
Mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；Use concentration
Sulphuric acid for 98wt% is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, obtains mixture iii after cooling；
By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 7】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 2g Glacial acetic acid magnesium and 0.3g Glacial acetic acid ferrum, 0.2g Glacial acetic acid nickel and 100g
Mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；Use concentration
Sulphuric acid for 98wt% is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, obtains mixture iii after cooling；
By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 8】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 2g Glacial acetic acid barium and 0.3g Glacial acetic acid ferrum, 0.2g Glacial acetic acid nickel and 100g
Mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；Use concentration
Sulphuric acid for 98wt% is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, obtains mixture iii after cooling；
By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 9】
By 40g2,3,6- TM-β-CD and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium and 0.3g Glacial acetic acid ferrum, 0.2g
Glacial acetic acid nickel and 100g mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain after cooling
Mixture ii；The sulphuric acid being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, cold
But obtain mixture iii afterwards；By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 10】
By 40g2, in the there-necked flask with reflux condensation mode, stirring at 80 DEG C adds for 3,6- tri- HP-β-CD and 160g isopropanol
Hot 30min, obtains mixture i after cooling；By 1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium and 0.3g Glacial acetic acid ferrum, 0.2g
Glacial acetic acid nickel and 100g mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain after cooling
Mixture ii；The sulphuric acid being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, cold
But obtain mixture iii afterwards；By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 11】
By 40g2,3,6- trimethyl-а-cyclodextrin and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium and 0.3g Glacial acetic acid ferrum, 0.2g
Glacial acetic acid nickel and 100g mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain after cooling
Mixture ii；The sulphuric acid being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, cold
But obtain mixture iii afterwards；By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 12】
By 40g2,3,6- trimethyls-gamma-cyclodextrin and 160g isopropanol in the there-necked flask with reflux condensation mode, agitating heating at 80 DEG C
30min, obtains mixture i after cooling；By 1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium and 0.3g Glacial acetic acid ferrum, 0.2g
Glacial acetic acid nickel and 100g mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain after cooling
Mixture ii；The sulphuric acid being 98wt% with concentration is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, cold
But obtain mixture iii afterwards；By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Comparative example 1】
By 200g2,3,6- trimethyl-а-cyclodextrin in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, cooling
After obtain mixture i；By 1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium and 0.3g Glacial acetic acid ferrum, 0.2g Glacial acetic acid nickel and
100g mixture i in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；With
Concentration is that the sulphuric acid of 98wt% is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, is mixed after cooling
Thing iii；By mixture iii at 80 DEG C, it is vacuum dried 30min, after cooling, obtain required catalyst.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Comparative example 2】
By 200g isopropanol in the there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain mixture i after cooling；
1g Glacial acetic acid magnesium, 1g Glacial acetic acid barium and 0.3g Glacial acetic acid ferrum, 0.2g Glacial acetic acid nickel and 100g mixture i are existed
In there-necked flask with reflux condensation mode, agitating heating 30min at 80 DEG C, obtain mixture ii after cooling；It is 98wt%'s with concentration
Sulphuric acid is added drop-wise in mixture ii under vigorous stirring, makes mixture pH be 6.0, obtains mixture iii after cooling；By mixture
Iii, at 80 DEG C, is vacuum dried 30min, obtains required catalyst after cooling.
Above-mentioned 1.0g catalyst is added in the autoclave putting into 1L in 100g methyl laurate while stirring；Autoclave
It is warming up to 80 DEG C, is vacuum dried 10min, then replaced 3 times with High Purity Nitrogen, be warming up to 150 DEG C, import EO, keeping temperature
At 150 DEG C, pressure is 144g, aging 30min in 0.4MPa, reaction 30min to EO addition, is cooled to room temperature and releases thing
Material, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various things in ethoxylated products
Matter content adopts GC-MS to analyze.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
The composition of table 1 catalyst of the present invention
Table 2 ethoxylated products analytical data
Claims (9)
1. the synthetic method of fatty acid methyl ester ethoxylation catalyst, comprises the following steps：
(1) by mass ratio be 1:(1～10) cyclodextrin and C1～C4Alcohol be mixed to get mixture i；
(2) alkali salt and VIII race's slaine are added in mixture i and are mixed to get mixture ii, wherein alkaline earth gold
Belonging to salt, VIII race's slaine and mixture i mass ratio is (0.1～0.3):(0.01～0.10):1；
(3) pH to 5～8 with adjusting mixture ii obtains mixture iii；
(4) mixture iii is vacuum dried below 100 DEG C and obtains described catalyst.
2. synthetic method as claimed in claim 1, is characterized in that described cyclodextrin structure leads to formula (I) as follows：
Wherein Z1、Z2、Z3Selected from H ,-CH3、-CH2-CHOH-CH3Base；N is selected from 6～12 integer.
3. synthetic method as claimed in claim 1, is characterized in that described alcohol is monohydric alcohol.
4. synthetic method as claimed in claim 1, is characterized in that described alcohol is C2～C4Dihydroxylic alcohols.
5. synthetic method as claimed in claim 1, is characterized in that described alkali salt and VIII race's slaine are independently selected from nitric acid
Salt, acetate or hydrochlorate.
6. synthetic method as claimed in claim 1, is characterized in that described alkaline-earth metal is selected from magnesium, calcium, strontium and barium extremely
Few one kind.
7. synthetic method as claimed in claim 1, is characterized in that at least one in described VIII race's metal chosen from Fe, cobalt, nickel.
8. the catalyst that in claim 1 to 7, the synthetic method described in any one obtains.
9. application in fatty acid methyl ester ethoxylation for the catalyst in claim 8.
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| CN1508110A (en) * | 2002-12-19 | 2004-06-30 | 中国石化上海石油化工股份有限公司 | Method for preparing alkoxy compound by oxyalkylation |
| CN1618514A (en) * | 2003-11-19 | 2005-05-25 | 中国石油化工股份有限公司 | Solid acid catalyst for hydration of epoxy ethane to produce ethandiol |
| CN101077480A (en) * | 2002-09-20 | 2007-11-28 | 美国拜尔公司 | Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto |
| CN102935375A (en) * | 2012-11-13 | 2013-02-20 | 上海焦化有限公司 | 3-methyl lactate hydrogenation catalyst and preparation method thereof |
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| EP1242463A1 (en) * | 1999-12-16 | 2002-09-25 | Eastman Chemical Resins, Inc. | Cyclodextrin ethers |
| CN101077480A (en) * | 2002-09-20 | 2007-11-28 | 美国拜尔公司 | Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto |
| CN1507950A (en) * | 2002-12-19 | 2004-06-30 | 中国石化上海石油化工股份有限公司 | Catalyst for oxyalkylation |
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