CN105498842B - Fatty acid methyl ester ethoxylation catalyst and its application - Google Patents
Fatty acid methyl ester ethoxylation catalyst and its application Download PDFInfo
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Abstract
The present invention relates to one kind for fatty acid methyl ester ethoxylation catalyst, the technical issues of EO distributions are wide, by-product is more in catalyst reaction product in the prior art is mainly solved.The present invention is by using fatty acid methyl ester ethoxylation catalyst, including following component：(a) alkaline earth metal carboxylation；(b) at least one of Zn salt and Cd salt；(c) technical solution of N hydroxy imides preferably solves the technical problem, in being produced available for fatty acid methyl ester ethoxylation.
Description
Technical field
The present invention relates to fatty acid methyl ester ethoxylation catalyst, preparation method and in fatty acid methyl ester ethoxylation
In application.
Background technology
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-the OCH similar to grease3, 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, replace toy, floor, textile garment that TX or NP handle etc. using FMEE, it is possible to reduce cause in exit procedure
Trade dispute.
Since fatty acid methyl ester is unlike aliphatic acid, fatty alcohol or fatty amine etc. are containing 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 hydrotalcites, adds simultaneously
Add a small amount of LiOH or SnO2It forms.For methyl laurate ethoxylation, LiOH or SnO is not added in discovery2When, unreacted EO
Content be more than 1.5%, EO profile exponents [EO adductions number account in total component in the component of ± 2 ranges of n (not including raw alcohol and
PEG content (wherein n is the EO adductions number of major constituent))], less than 70%；Add LiOH or SnO2Preferably, but catalyst amount
All more than 1.0%, reaction speed is slow.
United States Patent (USP) US5220246 (Process for Alkoxylation of Esters and Products
Produced Therefrom) a kind of active alkoxide calcium aluminium composite catalyst is disclosed for coconut acid methylester ethoxylation,
EO is averaged adduct number as 8, and polyethylene glycol is higher than 2.0% in product, and unreacted fatty acid methyl ester is more than 0.5%, and catalyst is used
Measure is 1.0%.
The shortcoming of the catalyst of the above-mentioned prior art is：EO distributions width, by-product are more in product.
Invention content
The first technical problem to be solved by the present invention is fatty acid methyl ester ethoxylated product in the prior art
The problem of middle EO distributions are wide, by-product is more, provides a kind of new catalyst for fatty acid methyl ester ethoxylation, this is urged
It is few with fatty acid methyl ester ethoxylated product EO narrowly distributings, by-product when agent is used for fatty acid methyl ester ethoxylation
The characteristics of.
The second technical problem to be solved by the present invention is the preparation method of one of above-mentioned technical problem catalyst.
The third technical problem to be solved by the present invention is one of above-mentioned technical problem catalyst 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,
Including following component：
(a) alkaline earth metal carboxylation；
(b) at least one of Zn salt and Cd salt；
(c) N- hydroxy imides.
As preferred technical solution, the catalyst forms by weight percentage is：(a) alkaline earth metal carboxylate, 20
~50%；(b) at least one of Zn salt and Cd salt amounts to 5~15%；(c) N- hydroxy imides, surplus.The Zn salt is for example
But it is not limited to ZnSO4, the Cd salt is such as, but not limited to CdSO4。
In above-mentioned technical proposal, at least one of described alkaline-earth metal preferred Mg, Ca, Sr and Ba.The alkaline-earth metal
More preferably simultaneously including Mg and Ba.As an example, including following component：N-hydroxysuccinimide and/or N- hydroxyls Malaysia acyl
Imines and Mg (AC)2With Ba (AC)2。
In above-mentioned technical proposal, the carboxylic acid is preferably C2~C4Carboxylic acid.
In above-mentioned technical proposal, the carboxylate is preferably monoacid or polyacid.
In above-mentioned technical proposal, the N- hydroxy imides are preferably by n-hydroxysuccinimide, N- hydroxyls Malaysia acyl
The object that imines, N- xenols dicarboximide, N- hydroxyl -1,8- naphthalimides, tert-butyl benzene imidodicarbonic diamide are formed
At least one of matter group.The N- hydroxy imides are more preferably simultaneously including n-hydroxysuccinimide and N- hydroxyls Malaysia acyl
Imines.As an example, including following component：N-hydroxysuccinimide and N- hydroxy maleimides and alkaline earth metal carboxylate
Salt Mg (AC)2(or Ba (AC)2)。
As the most preferred technical solution, the N- hydroxy imides are more preferably simultaneously including n-hydroxysuccinimide
With N- hydroxy maleimides, and the alkaline earth metal carboxylation more preferably simultaneously including Mg carboxylate and Ba carboxylate.
Only as an example, such as the catalyst includes following component：N-hydroxysuccinimide, N- hydroxy maleimides, Mg
(AC)2、Ba(AC)2With Zn salt.
To solve above-mentioned technical problem two, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of catalyst described in any one of case, includes the following steps：
(1) at least one of alkaline earth metal carboxylation, Zn salt and Cd salt and N- hydroxy imides are mixed with water
To mixture；
(2) by (1) obtained by mixture hydro-thermal process；
(3) it dries.
In above-mentioned technical proposal, in step (1) by quality ratio, preferred water:(alkaline earth metal carboxylation+Zn salt and Cd salt
At least one of+N- hydroxy imides)=(5~10):1.
In above-mentioned technical proposal, the temperature of step (2) hydro-thermal process is 50~100 DEG C.
In above-mentioned technical proposal, step (2) hydrothermal conditions preferably 2~8 hours.
To solve above-mentioned technical problem three, technical scheme is as follows：The technical side of one of above-mentioned technical problem
Application of the catalyst described in any one of case in fatty acid methyl ester ethoxylation.Fat described in the fatty acid methyl ester
Fat acid is preferably C4~C20Aliphatic acid；More preferable C6~C12Aliphatic acid.
The specifically used method of catalyst of the present invention can be but not limited to：By fatty acid methyl ester and catalyst (for fat
0.1~0.8wt% of sour methyl esters) it adds in autoclave, 60~80 DEG C are warming up under stirring, vacuumizes removing moisture and low boiling point
Substance；Then with the atmosphere in nitrogen displacement autoclave；Under 0.3~0.6 MPa of 150~180 DEG C of temperature and pressure, ring is added dropwise
Oxidative ethane (EO) extremely required amount；After 30~120min of aging, logical cooling water is cooled down, release, removes product.
Evaluation result shows that the fatty acid methyl ester ethoxylated products EO profile exponents of catalyst of the present invention are more than 80%,
For total byproduct (polyethylene glycol, unreacted fatty acid methyl ester) less than 1.0wt%, catalyst amount (accounts for total yield less than 1.0wt%
Quality).Therefore catalyst provided by the invention has the characteristics that ethoxylated products EO narrowly distributings, byproduct are few.
The preparation method of catalyst of the present invention, as optional specific embodiment, step is as follows：
(1) alkaline earth metal carboxylation and at least one of Zn salt and Cd salt are chosen and N- hydroxy imides is mixed with pure water
It closes, the quality of pure water is 5~10 times of above-mentioned solid material.
(2) by the mixture obtained by (1) at 50~100 DEG C, mixing speed is 600~1000rpm hydro-thermal process 2~8
Hour, it cools down, the sample tabletting that drying obtains, crush, screening, it is required catalyst to take its 100~200 mesh sample.
The present invention will be further described below by way of examples.
Specific embodiment
【Embodiment 1】
40g acetic anhydrides magnesium and the anhydrous ZnSO of 10g are weighed respectively4And 50gN- HOSu NHSs addition 800g is pure
In water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds stands 10 hours；Then it is small in 110 DEG C of dryings 18
When, the sample of 100-200 mesh is taken as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 2】
40g acetic anhydrides magnesium and the anhydrous ZnSO of 10g are weighed respectively4And 50g N- hydroxy maleimides addition 800g is pure
In water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds stands 10 hours；Then it is small in 110 DEG C of dryings 18
When, the sample of 100-200 mesh is taken as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 3】
40g acetic anhydrides barium and the anhydrous ZnSO of 10g are weighed respectively4And 50gN- HOSu NHSs addition 800g is pure
In water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds stands 10 hours；Then it is small in 110 DEG C of dryings 18
When, the sample of 100-200 mesh is taken as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 4】
40g acetic anhydrides barium and the anhydrous ZnSO of 10g are weighed respectively4And 50g N- hydroxy maleimides addition 800g is pure
In water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds stands 10 hours；Then it is small in 110 DEG C of dryings 18
When, the sample of 100-200 mesh is taken as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 5】
40g acetic anhydrides magnesium and the anhydrous ZnSO of 10g are weighed respectively4And 25gN- HOSu NHSs, 25g N- hydroxyls
Maleimide is added in 800g pure water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds, stands 10 hours；
Then it is 18 hours dry at 110 DEG C, the sample of 100-200 mesh is taken as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 6】
40g acetic anhydrides barium and the anhydrous ZnSO of 10g are weighed respectively4And 25gN- HOSu NHSs, 25g N- hydroxyls
Maleimide is added in 800g pure water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds, stands 10 hours；
Then it is 18 hours dry at 110 DEG C, the sample of 100-200 mesh is taken as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 7】
20g acetic anhydrides magnesium, 20g acetic anhydrides barium and the anhydrous ZnSO of 10g are weighed respectively4And 50gN- hydroxysuccinimidyl acyls
Imines is added in 800g pure water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds, stands 10 hours；Then exist
110 DEG C of dryings 18 hours take the sample of 100-200 mesh as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 8】
20g acetic anhydrides magnesium, 20g acetic anhydrides barium and the anhydrous ZnSO of 10g are weighed respectively4And 50g N- hydroxyls Malaysia acyl
Imines is added in 800g pure water, the hydro-thermal process 4 hours under the conditions of 85 DEG C, 800rpm mixing speeds, stands 10 hours；Then exist
110 DEG C of dryings 18 hours take the sample of 100-200 mesh as catalyst after tabletting, broken, screening.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
【Embodiment 9】
20g acetic anhydrides magnesium, 20g acetic anhydrides barium and the anhydrous ZnSO of 10g are weighed respectively4And 25gN- hydroxysuccinimidyl acyls
Imines, 25g N- hydroxy maleimides are added in 800g pure water, the hydro-thermal process 4 under the conditions of 85 DEG C, 800rpm mixing speeds
Hour, stand 10 hours；Then it is dried 18 hours at 110 DEG C, tabletting, the sample conduct for crushing, 100-200 mesh being taken after screening are urged
Agent.
Above-mentioned catalyst 0.5g is added in 100g methyl laurates, 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
Between 150~180 DEG C, pressure is 144g in 0.4MPa, reaction 30min to EO additions, and aging 30min is cooled to room temperature
Material is released, is weighed as 244g, obtains the lauric acid methyl ester ethoxylate that average EO adduct numbers are 7.Various substances in product
Content is analyzed using GC-MS.Compare for convenience, catalyst formulation is shown in Table 1, and analysis result is shown in Table 2.
The composition of 1 catalyst of the present invention of table
2 reaction product of table analyzes data
Claims (10)
1. fatty acid methyl ester ethoxylation catalyst, it is characterized in that the catalyst forms and is by weight percentage：
(a) alkaline earth metal carboxylation, 20~50%；
(b) at least one of Zn salt and Cd salt amounts to 5~15%；
(c) N- hydroxy imides, surplus.
2. catalyst as described in claim 1, it is characterized in that the alkaline-earth metal selects at least one of Mg, Ca, Sr and Ba.
3. catalyst as described in claim 1, it is characterized in that the carboxylic acid is C2~C4Carboxylic acid.
4. catalyst as described in claim 1, it is characterized in that the carboxylic acid is monoacid or polyacid.
5. catalyst as described in claim 1, it is characterized in that the N- hydroxy imides are n-hydroxysuccinimide, N- hydroxyls
Base maleimide, N- xenols dicarboximide, N- hydroxyl -1,8- naphthalimides, tert-butyl benzene imidodicarbonic diamide institute
At least one of substance group of composition.
6. the preparation method of catalyst described in any one of Claims 1 to 5, includes the following steps：
(1) at least one of alkaline earth metal carboxylation, Zn salt and Cd salt and N- hydroxy imides and water are mixed to get mixed
Close object；
(2) by (1) obtained by mixture hydro-thermal process；
(3) it dries.
7. preparation method as claimed in claim 6, it is characterized in that in step (1) by quality ratio, water:(alkaline earth metal carboxylate
At least one of salt+Zn salt and Cd salt+N- hydroxy imides)=(5~10):1.
8. preparation method as claimed in claim 6, it is characterized in that the temperature of step (2) hydro-thermal process is 50~100 DEG C.
9. preparation method as claimed in claim 8, it is characterized in that step (2) hydrothermal conditions are 2~8 hours.
10. application of any one of Claims 1 to 5 catalyst in fatty acid methyl ester ethoxylation.
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Citations (5)
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|---|---|---|---|---|
| CN1300641A (en) * | 1999-12-22 | 2001-06-27 | 辽阳利迪化学品有限公司 | Catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve |
| US6376721B1 (en) * | 2001-01-19 | 2002-04-23 | Rhodia, Inc. | Process for alkoxylation in the presence of rare earth triflimides |
| CN1451476A (en) * | 2003-03-28 | 2003-10-29 | 中国日用化学工业研究院 | Catalyst for ethoxylation and use thereof |
| JP2005046749A (en) * | 2003-07-29 | 2005-02-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Catalyst for alkoxylation and method for manufacturing alkylene oxide addition product using it |
| CN101374599A (en) * | 2004-08-26 | 2009-02-25 | 胡茨曼石油化学公司 | Alkaline earth-based alkoxylation catalysts |
-
2014
- 2014-09-25 CN CN201410497661.XA patent/CN105498842B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300641A (en) * | 1999-12-22 | 2001-06-27 | 辽阳利迪化学品有限公司 | Catalyst for alkoxylating solid acid with cationic bonded chromatography column molecular sieve |
| US6376721B1 (en) * | 2001-01-19 | 2002-04-23 | Rhodia, Inc. | Process for alkoxylation in the presence of rare earth triflimides |
| CN1451476A (en) * | 2003-03-28 | 2003-10-29 | 中国日用化学工业研究院 | Catalyst for ethoxylation and use thereof |
| JP2005046749A (en) * | 2003-07-29 | 2005-02-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Catalyst for alkoxylation and method for manufacturing alkylene oxide addition product using it |
| CN101374599A (en) * | 2004-08-26 | 2009-02-25 | 胡茨曼石油化学公司 | Alkaline earth-based alkoxylation catalysts |
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