CN106423270B - The synthetic method of fatty acid methyl ester ethoxylation catalyst - Google Patents
The synthetic method of fatty acid methyl ester ethoxylation catalyst Download PDFInfo
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Abstract
The present invention relates to the synthetic method of fatty acid methyl ester ethoxylation catalyst, solve the problems, such as that EO profile exponent is low in catalyst reaction product existing in the prior art.Use the following steps are included: (1) by mass ratio for 1:(1~10) cyclodextrin and C1~C4Alcohol be mixed to get mixture i；(2) alkali salt and VIII race's metal salt are added in mixture i and are mixed to get mixture ii, wherein alkali salt, VIII race's metal salt and mixture i mass ratio are (0.1~0.3): (0.01~0.10): 1；(3) pH to 5~8 for adjusting mixture ii obtains mixture iii；(4) mixture iii is obtained into the technical solution of the catalyst in 100 DEG C or less vacuum drying, preferably solves the technical problem, can be used for the reaction of fatty acid methyl ester ethyoxyl.
Description
Technical field
The present invention relates to a kind of synthetic methods for fatty acid methyl ester ethoxylation catalyst.
Background technique
Fatty acid methyl ester ethoxy compound (ethoxylated fatty acid methyl esters), referred to as
FMEE is a kind of ester-ether type nonionic surfactant of novel bi-end-blocking.Due to fatty acid methyl ester ethoxy compound one end
With-OCH3 similar with grease, according to the principle of similar compatibility, compared with traditional fatty acid polyether, aliphatic alcohol polyether etc.,
There is stronger dirt-removing power, there is good water solubility, the advantages that fusing point is low, and emulsion dispersion ability is strong, and foam is few；In addition the product is easy
Degradation, is a kind of real environment-friendly type surfactant.Fatty acid methyl ester chemical combination object is widely applied to leather, weaving, change
In cosmetic industry.FMEE, close to TX, NP and OP series containing APEO, is strict with environmental protection in foreign countries in various performances
Background under, toy, floor, textile garment etc. for using FMEE that TX or NP is replaced to handle, it is possible to reduce cause in exit procedure
Trade dispute.
Due to fatty acid methyl ester unlike fatty acid, fatty alcohol or fatty amine etc. contain active hydrogen, urged with traditional soda acid
Agent is difficult ethoxylation (ethyleneoxide addition, i.e. EO addition), i.e., enabled, 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 exists
0.3MPa or so, catalyst amount 0.1~1.0%
United States Patent (USP) US6008392 (Process for Preparing Alkoxylated Fatty Acid Alkyl
Esters a kind of fatty acid methyl ester ethoxylation catalyst) is disclosed, catalyst mainly based on Al/Mg hydrotalcite, adds simultaneously
Add a small amount of LiOH or SnO2It constitutes.For methyl laurate ethoxylation, LiOH or SnO is not added in discovery2When, unreacted EO
Content be more than 1.5%, EO profile exponent [EO adduction number account in total component in the component of ± 2 range of n (do not include raw alcohol and
PEG content (the wherein EO adduction number that n is major constituent))], less than 70%；Add LiOH or SnO2Preferably, but catalyst amount
All 1.0% or more, reaction speed is slow.
United States Patent (USP) US5220246 (Process for Alkoxylation of Esters and Products
Produced Therefrom) disclose a kind of active alkoxide calcium aluminium composite catalyst for coconut acid methylester ethoxylation,
The EO adduct number that is averaged is 8, and polyethylene glycol is higher than 2.0% in product, and unreacted fatty acid methyl ester is greater than 0.5%, and catalyst is used
Amount is 1.0%.
The shortcoming of the catalyst of the above-mentioned prior art is: EO profile exponent is low in product, by-product is more.
Summary of the invention
The first technical problem to be solved by the present invention is second after catalyst ethoxylation existing in the prior art
EO profile exponent is low in oxygroup product, the problem more than by-product, provides a kind of new fatty acid methyl ester ethoxylation catalyst
Synthetic method, EO in ethoxylated products when this method has obtained catalyst for fatty acid methyl ester ethoxylation
The few feature of narrowly distributing, by-product.
The second technical problem to be solved by the present invention is the catalysis that synthetic method described in one of above-mentioned technical problem obtains
Agent.
The third technical problem to be solved by the present invention is two catalyst of above-mentioned technical problem in fatty acid methyl ester
Application in ethoxylation.
One of to solve above-mentioned technical problem, technical scheme is as follows: fatty acid methyl ester ethoxylation catalyst
Synthetic method, including following preparation step:
(1) it is 1:(1~10 by mass ratio) cyclodextrin and C1~C4Alcohol be mixed to get mixture i；For convenient for mixing, can
The viscosity of cyclodextrin is reduced in a manner of through heating；
(2) alkali salt and VIII race's metal salt are added in mixture i and are mixed to get mixture ii, wherein alkaline earth gold
Belonging to salt, VIII race's metal salt and mixture i mass ratio is (0.1~0.3): (0.01~0.10): 1；
(3) mixture iii is obtained with the pH to 5~8 for adjusting mixture ii；
(4) mixture iii is obtained into the catalyst in 100 DEG C or less vacuum drying.
For the mixing velocity for accelerating above-mentioned steps (1) and/or step (2), preferably mixed under heating state.Above-mentioned technology
In scheme, when step (3) adjusts the pH of mixture ii, it is preferred to use the concentrated sulfuric acid, most preferably using concentration for 98wt% is pH tune
Save agent.
In above-mentioned technical proposal, it is as follows that the cyclodextrin structure leads to formula (I):
Wherein Z1、Z2、Z3Selected from H ,-CH3、-CH2-CHOH-CH3Base, preferably-CH3；N be selected from 6~12 integer, preferably 6
~8 integer, more preferable 7.It is related in place of cyclodextrin in the embodiment of the present invention and comparative example, n is 7.
In above-mentioned technical proposal, the alcohol can be monohydric alcohol.As an example, the alcohol can be selected from methanol, second
Alcohol, normal propyl alcohol, isopropanol, n-butyl alcohol, 2- butanol, 2- methyl-1-propyl alcohol or 2- methyl-2-propanol.
In above-mentioned technical proposal, the alcohol is C2~C4Dihydric alcohol.As an example, the alcohol can be selected from second two
Alcohol, 1,2-PD, 1,3-PD.
In above-mentioned technical proposal, the alkali salt and VIII race's metal salt preferably independently are selected from nitrate, acetate or salt
Hydrochlorate, more preferable acetate.
In above-mentioned technical proposal, the alkaline-earth metal preferably is selected from least one of magnesium, calcium, strontium and barium.The alkali
Than individually including that magnesium is good without including barium effect when earth metal includes simultaneously magnesium and barium, also than individually including barium without including that magnesium is imitated
Fruit is good.
In above-mentioned technical proposal, VIII race metal salt preferably is selected from least one of iron, cobalt, nickel.VIII race metal
Than individually including that iron is good without including nickel effect when simultaneously including iron and nickel, also than individually including that nickel is good without including iron effect.
As the most preferred technical solution: the cyclodextrin is 2,3,6- trimethyl-β-cyclodextrin (i.e. Z1、Z2、Z3
For-CH3)；The alkaline-earth metal includes magnesium and barium simultaneously, and VIII race metal includes simultaneously iron and nickel.
In above-mentioned technical proposal, step (1) cyclodextrin and C1~C4Alcohol mass ratio be preferably 1:(2.5~5).Step
(3) the preferred pH of pH value in is more than or equal to 5 and less than 7, and more preferable pH is 5.5~6.5.Add described in step (2) in step (1)
Hot temperature is preferably 60~120 DEG C；Heating time is preferably 10~60min.Vacuum drying temperature described in step (4) is preferred
For 50 DEG C more than or lower than 100 DEG C, the dry time is preferably 10~60min.
To solve above-mentioned technical problem two, technical scheme is as follows: any one of one of above-mentioned technical problem
The catalyst that synthetic method described in technical solution obtains.
To solve above-mentioned technical problem three, technical scheme is as follows: the catalysis of the two of above-mentioned technical problem
Application of the agent in fatty acid methyl ester ethoxylation.
Catalyst of the invention is evaluated according to following process: by 100~300g fatty acid methyl ester and catalyst (for
0.1~0.8wt% of fatty acid methyl ester) it is added in 1 liter of stainless steel autoclave with stirring slurry, 80 are warming up under stirring
DEG C, 10min is vacuumized, moisture and low-boiling point material are removed；Then it is replaced at least 3 times with nitrogen；In 150~180 DEG C of temperature and
Under 0.3~0.6MPa of pressure, ethylene oxide (EO) is continuously added dropwise to required amount；After aging 30min, it is cold to lead to cooling water progress
But, release removes product, weighing, analysis.
Evaluation result shows that the fatty acid methyl ester ethoxylated products EO profile exponent of catalyst of the present invention is greater than 80%,
Total byproduct (polyethylene glycol or polypropylene glycol, unreacted fatty acid methyl ester) is less than 1.0wt%, and catalyst amount is less than
1.0wt% (accounts for total yield quality).Therefore catalyst provided by the invention has ethoxylated products EO profile exponent height, by-product
The few feature of product.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；2g acetic anhydride magnesium, 0.5g acetic anhydride iron and 100g mixture i are existed
In three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C obtains mixture ii after cooling；It is 98wt% with concentration
Sulfuric acid be added drop-wise in mixture ii under vigorous stirring, make mixture pH 6.0, obtain mixture iii after cooling；It will mixing
Object iii is dried in vacuo 30min, obtains required catalyst after cooling at 80 DEG C.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 2]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160 isopropanols are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；2g acetic anhydride magnesium, 0.5g acetic anhydride nickel and 100g mixture i are existed
In three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C obtains mixture ii after cooling；It is 98wt% with concentration
Sulfuric acid be added drop-wise in mixture ii under vigorous stirring, make mixture pH 6.0, obtain mixture iii after cooling；It will mixing
Object iii is dried in vacuo 30min, obtains required catalyst after cooling at 80 DEG C.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 3]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；2g acetic anhydride barium, 0.5g acetic anhydride iron and 100g mixture i are existed
In three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C obtains mixture ii after cooling；It is 98wt% with concentration
Sulfuric acid be added drop-wise in mixture ii under vigorous stirring, make mixture pH 6.0, obtain mixture iii after cooling；It will mixing
Object iii is dried in vacuo 30min, obtains required catalyst after cooling at 80 DEG C.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 4]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；2g acetic anhydride magnesium, 0.5g acetic anhydride nickel and 100g mixture i are existed
In three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C obtains mixture ii after cooling；It is 98wt% with concentration
Sulfuric acid be added drop-wise in mixture ii under vigorous stirring, make mixture pH 6.0, obtain mixture iii after cooling；It will mixing
Object iii is dried in vacuo 30min, obtains required catalyst after cooling at 80 DEG C.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 5]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；By 1g acetic anhydride magnesium, 1g acetic anhydride barium, 0.5g acetic anhydride iron and
100g mixture i is in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, obtains mixture ii after cooling；With
Concentration is that the sulfuric acid of 98wt% is added drop-wise under vigorous stirring in mixture ii, makes mixture pH 6.0, is mixed after cooling
Object iii；By mixture iii at 80 DEG C, it is dried in vacuo 30min, obtains required catalyst after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 6]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；By 1g acetic anhydride magnesium, 1g acetic anhydride barium and 0.5g acetic anhydride nickel
With 100g mixture i in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C obtains mixture ii after cooling；
The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, is made mixture pH 6.0, is mixed after cooling
Close object iii；By mixture iii at 80 DEG C, it is dried in vacuo 30min, obtains required catalyst after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 7]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；By 2g acetic anhydride magnesium and 0.3g acetic anhydride iron, 0.2g acetic anhydride
Nickel and 100g mixture i are in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, obtain mixture after cooling
ii；The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, is made mixture pH 6.0, is obtained after cooling
To mixture iii；By mixture iii at 80 DEG C, it is dried in vacuo 30min, obtains required catalyst after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 8]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；By 2g acetic anhydride barium and 0.3g acetic anhydride iron, 0.2g acetic anhydride
Nickel and 100g mixture i are in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, obtain mixture after cooling
ii；The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, is made mixture pH 6.0, is obtained after cooling
To mixture iii；By mixture iii at 80 DEG C, it is dried in vacuo 30min, obtains required catalyst after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 9]
By 40g2,3,6- trimethyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；By 1g acetic anhydride magnesium, 1g acetic anhydride barium and 0.3g acetic anhydride
Iron, 0.2g acetic anhydride nickel and 100g mixture i are in the three-necked flask with reflux condensation mode, and agitating and heating 30min, cold at 80 DEG C
But mixture ii is obtained afterwards；The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, makes mixture pH
It is 6.0, obtains mixture iii after cooling；By mixture iii at 80 DEG C, it is dried in vacuo 30min, is obtained after cooling required
Catalyst.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 10]
By 40g2,3,6- tri- hydroxypropyl-β-cyclodextrins and 160g isopropanol are in the three-necked flask with reflux condensation mode, and 80 DEG C
Lower agitating and heating 30min obtains mixture i after cooling；By 1g acetic anhydride magnesium, 1g acetic anhydride barium and 0.3g acetic anhydride
Iron, 0.2g acetic anhydride nickel and 100g mixture i are in the three-necked flask with reflux condensation mode, and agitating and heating 30min, cold at 80 DEG C
But mixture ii is obtained afterwards；The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, makes mixture pH
It is 6.0, obtains mixture iii after cooling；By mixture iii at 80 DEG C, it is dried in vacuo 30min, is obtained after cooling required
Catalyst.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 11]
By 40g2,3,6- trimethyl-а-cyclodextrin and 160g isopropanol are in the three-necked flask with reflux condensation mode, at 80 DEG C
Agitating and heating 30min obtains mixture i after cooling；By 1g acetic anhydride magnesium, 1g acetic anhydride barium and 0.3g acetic anhydride
Iron, 0.2g acetic anhydride nickel and 100g mixture i are in the three-necked flask with reflux condensation mode, and agitating and heating 30min, cold at 80 DEG C
But mixture ii is obtained afterwards；The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, makes mixture pH
It is 6.0, obtains mixture iii after cooling；By mixture iii at 80 DEG C, it is dried in vacuo 30min, is obtained after cooling required
Catalyst.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[embodiment 12]
By 40g2,3,6- trimethyls-gamma-cyclodextrin and 160g isopropanol are in the three-necked flask with reflux condensation mode, and 80 DEG C
Lower agitating and heating 30min obtains mixture i after cooling；By 1g acetic anhydride magnesium, 1g acetic anhydride barium and 0.3g acetic anhydride
Iron, 0.2g acetic anhydride nickel and 100g mixture i are in the three-necked flask with reflux condensation mode, and agitating and heating 30min, cold at 80 DEG C
But mixture ii is obtained afterwards；The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, makes mixture pH
It is 6.0, obtains mixture iii after cooling；By mixture iii at 80 DEG C, it is dried in vacuo 30min, is obtained after cooling required
Catalyst.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[comparative example 1]
By 200g2,3,6- trimethyl-а-cyclodextrin is in the three-necked flask with reflux condensation mode, agitating and heating at 80 DEG C
30min obtains mixture i after cooling；By 1g acetic anhydride magnesium, 1g acetic anhydride barium and 0.3g acetic anhydride iron, 0.2g without
Water acetic acid nickel and 100g mixture i are in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, obtain after cooling
Mixture ii；The sulfuric acid for being 98wt% with concentration is added drop-wise under vigorous stirring in mixture ii, makes mixture pH 6.0, cold
But mixture iii is obtained afterwards；By mixture iii at 80 DEG C, it is dried in vacuo 30min, obtains required catalyst after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
[comparative example 2]
By 200g isopropanol in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C is mixed after cooling
Close object i；1g acetic anhydride magnesium, 1g acetic anhydride barium and 0.3g acetic anhydride iron, 0.2g acetic anhydride nickel and 100g are mixed
Object i is in the three-necked flask with reflux condensation mode, agitating and heating 30min at 80 DEG C, obtains mixture ii after cooling；It is with concentration
The sulfuric acid of 98wt% is added drop-wise under vigorous stirring in mixture ii, is made mixture pH 6.0, is obtained mixture iii after cooling；
By mixture iii at 80 DEG C, it is dried in vacuo 30min, obtains required catalyst after cooling.
Above-mentioned 1.0g catalyst is added in 100g methyl laurate, is put into the autoclave of 1L while stirring；It is high
Pressure kettle is warming up to 80 DEG C, is dried in vacuo 10min, is then replaced 3 times with High Purity Nitrogen, is warming up to 150 DEG C, imports EO, keeps temperature
At 150 DEG C, pressure is in 0.4MPa, and reacting 30min to EO additional amount is 144g, and aging 30min is cooled to room temperature releasing material,
It is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct number is 7.Various substances contain in ethoxylated products
Amount is analyzed using GC-MS.
Compare for convenience, catalyst formulation is shown in Table 1, and analysis the results are shown in Table 2.
The composition of the catalyst of the present invention of table 1
2 ethoxylated products of table analyze data
Claims (7)
1. application of the fatty acid methyl ester ethoxylation catalyst in fatty acid methyl ester ethoxylation, characterized in that the fat
Sour methyl esters ethoxylation catalyst includes the following steps obtained:
(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 metal salt are added in mixture i and are mixed to get mixture ii, wherein alkaline-earth metal
Salt, VIII race's metal salt and mixture i mass ratio are (0.1~0.3): (0.01~0.10): 1；
(3) pH to 5~8 for adjusting mixture ii obtains mixture iii；
(4) mixture iii is obtained into the catalyst in 100 DEG C or less vacuum drying.
2. application as described in claim 1, it is characterized in that the logical formula (I) of the cyclodextrin structure is as follows:
Wherein Z1、Z2、Z3It is independently selected from H ,-CH3、-CH2-CHOH-CH3Base；N is selected from 6~12 integer.
3. application as described in claim 1, it is characterized in that the alcohol is monohydric alcohol.
4. application as described in claim 1, it is characterized in that the alcohol is C2~C4Dihydric alcohol.
5. application as described in claim 1, it is characterized in that the alkali salt and VIII race's metal salt be independently selected from nitrate,
Acetate or hydrochloride.
6. application as described in claim 1, it is characterized in that the alkaline-earth metal in magnesium, calcium, strontium and barium at least one
Kind.
7. application as described in claim 1, it is characterized in that VIII race metal is selected from least one of iron, cobalt, nickel.
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| EP1242463A1 (en) * | 1999-12-16 | 2002-09-25 | Eastman Chemical Resins, Inc. | Cyclodextrin ethers |
| 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 |
| 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 |
| 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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2015
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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 |
| 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 |
| 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 |
| 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 |
| 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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