CN104588112B - Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof - Google Patents
Magnetic bidentate nitrogen-containing tin ligand catalyst and preparation method thereof Download PDFInfo
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- CN104588112B CN104588112B CN201510029516.3A CN201510029516A CN104588112B CN 104588112 B CN104588112 B CN 104588112B CN 201510029516 A CN201510029516 A CN 201510029516A CN 104588112 B CN104588112 B CN 104588112B
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Abstract
The invention discloses a magnetic bidentate nitrogen-containing tin ligand catalyst and a preparation method thereof, relates to a catalyst for esterification and a preparation method of the catalyst and aims at solving the problems that the traditional non-homogeneous phase tin catalyst is difficult to recover after catalytic reaction and remains in a product. The preparation method comprises the following steps: 1, preparing a nitrogen ligand containing an active group; 2, preparing a magnetic bidentate nitrogen-containing ligand; and 3, preparing a magnetic bidentate nitrogen-containing tin ligand. According to the magnetic bidentate nitrogen-containing tin ligand catalyst and the preparation method thereof disclosed by the invention, a tin ligand catalyst with high activity is fixed to nanometer iron oxide particles with superparamagnetism, so that the catalyst can be separated from a reaction system by virtue of an external magnetic field after reaction is finished and can be recycled, and the amount of residues of the catalyst in the product is reduced.
Description
Technical field
The present invention relates to a kind of catalyst for esterification and preparation method thereof, and in particular to one kind is used for stearic acid
With the catalyst of nitrogenous tin part of the esterification of ethylene glycol and preparation method thereof.
Background technology
Esterification is the important reaction of a class in organic synthesis, is produced using the esterification of stearic acid and ethylene glycol
The glycol stearate for going out is a kind of chemical additives, in being widely used in various detergent products.Organotin catalysts have
There is very high catalysis activity, the glycol stearate produced during as catalyst has the advantages that color and luster is good, purity is high.But
Catalyst can be remained in the product, be not easily recycled utilization.
The content of the invention
The purpose of the present invention is that for the deficiencies in the prior art, there is provided a kind of nitrogenous tin ligand catalyst of magnetic bidentate
And preparation method thereof, solve the problems, such as that organotin catalysts are easily remained, are not easily recycled in existing esterification.
The nitrogenous tin ligand catalyst of magnetic bidentate that the present invention is provided, its structural formula is：
,
In formula, n is CH for 1～5, R3(CH2)m, wherein m=0～5；FexOyFor Fe2O3Or Fe3O4。
It is prepared by the following method and obtains：
（1）Prepare nitrogen ligand containing active group：Silane coupler and the reaction of alkyl diamine agitating heating are obtained containing activity
Group nitrogen ligand；Wherein the ratio of the amount of the material of silane coupler and alkyl diamine is 1～5 ︰ 1, is heated with stirring to 70 DEG C～150
DEG C, then react 2～10 hours at 70 DEG C～150 DEG C, through rotating pressure-decreasing distillation, obtain final product nitrogen ligand containing active group；Enter
The optimal technical scheme of one step is, the ratio of the amount of the material of silane coupler and alkyl diamine is 2 ︰ 1, reaction temperature is 90 DEG C～
100 DEG C, the reaction time is 6～8 hours；Wherein, silane coupler is selected from vinyltrimethoxy silane, 3- chloropropyl trimethoxies
Base silane, 3- chloropropyl triethoxysilanes and 3- bromopropyl trimethoxy silanes, alkyl diamine is selected from 1,3 propane diamine, Isosorbide-5-Nitrae fourth
Diamines and 1,5 pentanediamines.
（2）Prepare magnetic bidentate containing n-donor ligand：Under nitrogen protection, active group nitrogen ligand and magnetic Fe will be containedxOyNanometer
Particle is added sequentially in solvent I, and the stirring under conditions of temperature is for 70 DEG C～150 DEG C obtains magnetic bidentate containing n-donor ligand, returns
Stream 8 ~ 36 hours, is cooled to room temperature, is separated magnetic bidentate containing n-donor ligand with solvent I using externally-applied magnetic field, and first is then used respectively
Benzene or ethanol are washed 3～6 times, and then drying under reduced pressure, obtains magnetic bidentate containing n-donor ligand, wherein nitrogen ligand containing active group with
FexOyThe mol ratio of nano particle is 3～10 ︰ 1, and the mol ratio of nitrogen ligand containing active group and solvent I is 1 ︰ 120 ~ 180, solvent
I is toluene or absolute ethyl alcohol, FexOyFor Fe2O3Or Fe3O4；Further optimal technical scheme is, nitrogen ligand containing active group with
FexOyThe mol ratio of nano particle is 4 ︰ 1, and the mol ratio of nitrogen ligand containing active group and solvent I is 1 ︰ 140, the temperature strip of stirring
Part is 100 DEG C, is stirred at reflux the time for 18h.
（3）Prepare the nitrogenous tin part of magnetic bidentate：Under nitrogen protection, by R2SnCl2With magnetic bidentate nitrogen ligands according to rubbing
You are added in solvent II than the ratio for 0.8 ~ 1.8 ﹕ 1, are stirred at reflux 8 ~ 36 hours in the case where temperature is for 50～80 DEG C, are cooled to
Room temperature is separated the nitrogenous tin part of magnetic bidentate with solvent II using externally-applied magnetic field, is washed with ethanol 3 times, and drying under reduced pressure is obtained final product
The nitrogenous tin ligand catalyst of magnetic bidentate；Wherein solvent II be ethanol, propyl alcohol or butanol, R2SnCl2Middle R is CH3(CH2)m, m=0
～5.Further optimal technical scheme is, R2SnCl2It is 1.1 ︰ 1 with the mol ratio of magnetic bidentate containing n-donor ligand, the temperature of stirring
Condition is 70 DEG C, is stirred at reflux the time for 24h.
The present invention prepares the reaction equation of the nitrogenous tin ligand catalyst of magnetic bidentate：
Wherein, R is CH3(CH2)m, wherein m is=0～5.
The invention has the beneficial effects as follows：The nitrogenous tin ligand catalyst of magnetic bidentate of the present invention is with the magnetic with superparamagnetism
Property particle as carrier, the magnetic particle of superparamagnetism does not have magnetic when the external world is without magnetic field, it is extraneous apply magnetic field when quilt
Magnetize and there is magnetic, magnetic disappears when magnetic field is withdrawn from.By the upper nitrogen tin part of silane coupler load, the catalyst
During the reaction of stearic acid and ethylene glycol, there is higher catalysis activity at a lower temperature, product purity is more than 99%, color and luster compared with
It is shallow.After the catalyst of the present invention is reclaimed, five catalysis activities are recycled without substantially reduction, product yield is still more than 90%.Profit
The catalyst prepared with the inventive method can be magnetized by externally-applied magnetic field, and when externally-applied magnetic field is removed, magnetic disappears, therefore the present invention
Magnetic bidentate nitrogen tin ligand catalyst can realize being separated with reaction system in externally-applied magnetic field, relative to other catalyst
Separation method, with simple timesaving advantage, and reduce catalyst residual in the product.
The magnetic bidentate nitrogen tin ligand catalyst of the present invention is used to be catalyzed the esterification of stearic acid and ethylene glycol.
Specific embodiment
In order to be more clearly understood from the purpose of the present invention, technical scheme and beneficial effect, the present invention is done into one below
The explanation of step, but not by protection scope of the present invention limit in the examples below.
Embodiment one：
（1）Preparation containing active group nitrogen ligand：Weigh silane coupler and alkyl diamine, wherein silane coupler and alkane
The ratio of the amount of the material of base diamines is 1 ﹕ 1, is heated with stirring to 70 DEG C～150 DEG C, and then reaction 2 ~ 10 is little at 70 DEG C～150 DEG C
When, through rotating pressure-decreasing distillation, obtain final product the nitrogen ligand containing active group；Wherein silane coupler is selected from vinyl trimethoxy silicon
Alkane, 3- r-chloropropyl trimethoxyl silanes, 3- chloropropyl triethoxysilanes and 3- bromopropyl trimethoxy silanes, alkyl diamine choosing
From 1,3 propane diamine, Isosorbide-5-Nitrae butanediamine or 1,5 pentanediamines
（2）The preparation of magnetic bidentate containing n-donor ligand：Under nitrogen protection, by the nitrogen ligand containing active group and magnetic FexOy
Nano particle is added sequentially in solvent I, is stirred under conditions of temperature is for 70 DEG C～150 DEG C, is flowed back 8 ~ 36 hours, is cooled to
Room temperature, is separated magnetic bidentate nitrogen ligands with solvent I using externally-applied magnetic field, then with toluene, ethanol washs 3～6 respectively again
Secondary, then drying under reduced pressure, obtains magnetic bidentate nitrogen ligands, wherein the nitrogen ligand containing active group and FexOyNano particle mol ratio
For 3：1, the nitrogen ligand containing active group is 1 with the mol ratio of solvent I：120, solvent I is toluene or absolute ethyl alcohol, FexOyFor
Fe2O3Or Fe3O4；
（3）The preparation of the nitrogenous tin part of magnetic bidentate：Under nitrogen protection, by R2SnCl2Press with magnetic bidentate containing n-donor ligand
It is added in solvent II according to the ratio that mol ratio is 0.8 ﹕ 1, is stirred at reflux 8 ~ 36 hours in the case where temperature is for 50～80 DEG C, is cooled to
Room temperature is separated magnetic bidentate nitrogen tin part and solvent using externally-applied magnetic field, is washed with ethanol 3 times, and drying under reduced pressure obtains final product magnetic
Property bidentate nitrogen tin ligand catalyst.Wherein solvent II is ethanol, propyl alcohol or butanol.
Embodiment two：
The present embodiment is identical with embodiment one, except for the difference that step（1）The material of middle silane coupler and alkyl diamine
The ratio of amount is 5 ﹕ 1.
Embodiment three：
The present embodiment is identical with embodiment one, except for the difference that step（1）The material of middle silane coupler and alkyl diamine
The ratio of amount is 2 ﹕ 1.
Example IV：
The present embodiment is identical with embodiment three, except for the difference that step（1）The temperature of middle agitating heating is 90 DEG C～100 DEG C,
Reaction time is 6 ~ 8 hours.
Embodiment five：
The present embodiment is identical with embodiment two, except for the difference that step（2）In containing active group nitrogen ligand and FexOyNanometer
Particle mol ratio is 10：1, the nitrogen ligand containing active group is 1 with the mol ratio of solvent I：180.
Embodiment six：
The present embodiment is identical with embodiment three, except for the difference that step（2）In containing active group nitrogen ligand and FexOyNanometer
Particle mol ratio is 4：1, the nitrogen ligand containing active group is 1 with the mol ratio of solvent I：140.
Embodiment seven：
The present embodiment is identical with embodiment six, except for the difference that step（2）The temperature conditionss of middle stirring are 100 DEG C, are stirred back
The stream time is 18h.
Embodiment eight：
The present embodiment is identical with embodiment five, except for the difference that step（3）Middle R2SnCl2With rubbing for magnetic bidentate containing n-donor ligand
You are than being 1.8 ﹕ 1.
Embodiment nine：
The present embodiment is identical with embodiment six, except for the difference that step（3）Middle R2SnCl2With rubbing for magnetic bidentate containing n-donor ligand
You are than being 1.1 ﹕ 1.
Embodiment ten：
The present embodiment is identical with embodiment nine, except for the difference that step（3）The temperature conditionss of middle stirring are 70 DEG C, are stirred at reflux
Time is 24h.
Beneficial effects of the present invention are verified using tests below：
Using the esterification of the nitrogenous tin ligand catalyst catalysis stearic acid of magnetic bidentate obtained by above-described embodiment and ethylene glycol
React, experimental procedure and result are as described below：
Experimental procedure：0.9 mol stearic acid is added to being equipped with the there-necked flask of paddle, thermometer and division box, 0.5
Mol ethylene glycol and 0.1% (gross mass) catalyst, are passed through nitrogen, are heated to 180 DEG C, and using division box dereaction is removed in time
The water of middle generation.Reaction stops reaction after 6 hours, uses high performance liquid chromatography detection result.As a result show that conversion ratio is more than 99%.
Using the reaction of the nitrogenous tin ligand catalyst catalysis stearic acid of magnetic bidentate obtained by above-described embodiment and ethylene glycol
When, after catalyst is reclaimed, to reuse 5 times, catalysis activity has no and is decreased obviously, and experimental procedure and result are as described below：
Experimental procedure：0.9 mol stearic acid is added to being equipped with the there-necked flask of paddle, thermometer and division box, 0.5
Mol ethylene glycol and 0.1% (gross mass) catalyst, are passed through nitrogen, are heated to 180 DEG C, and using division box dereaction is removed in time
The water of middle generation.Reaction stops reaction after 6 hours.After reaction terminates, an additional magnet, by the absorption of magnetic bidentate nitrogen tin catalyst
In there-necked flask bottom, upper solution is poured out, use high performance liquid chromatography detection result.Magnetic bidentate nitrogen tin catalyst is washed with ethanol
Drying under reduced pressure after washing 3 times, continuation is tested next time.
As described above, repeat carrying out 4 experiments, the catalyst for reclaiming was tested in experiment every time using last time.
Present embodiment gained magnetic bidentate nitrogen tin catalyst is reused five times, and product yield is above 90%, catalyst
Catalysis activity have no substantially reduction, product yield is as shown in Table 1.
The magnetic bidentate nitrogen tin ligand catalyst of the present invention is using the magnetic particle with superparamagnetism as carrier, superparamagnetic
Property magnetic particle there is no magnetic when the external world is without magnetic field, it is extraneous apply magnetic field when be magnetized and there is magnetic, work as magnetic field
Magnetic disappears when withdrawing from.By the upper nitrogen tin part of silane coupler load, the reaction of the catalyst stearic acid and ethylene glycol
When, there is higher catalysis activity at a lower temperature, product purity is more than 99%, and color and luster is shallower.The catalyst of the present invention is reclaimed
Afterwards, five catalysis activities are recycled without substantially reduction, product yield is still more than 90%.Using prepared by the inventive method urging
Agent can be magnetized by externally-applied magnetic field, and when externally-applied magnetic field is removed, magnetic disappears, therefore the magnetic bidentate nitrogen tin part of the present invention is urged
Agent can be realized being separated with reaction system in externally-applied magnetic field, relative to the separation method of other catalyst, with simple
Timesaving advantage, and reduce catalyst residual in the product.
Claims (10)
1. the nitrogenous tin ligand catalyst of a kind of magnetic bidentate, it is characterised in that：Its structural formula is：
,
In formula, n is CH for 1～5, R3(CH2)m, wherein m=0～5；FexOyFor Fe2O3Or Fe3O4。
2. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 1, it is characterised in that：Bag
Include following preparation process：
（1）Prepare nitrogen ligand containing active group：Jing rotating pressure-decreasings after silane coupler and the reaction of alkyl diamine agitating heating are steamed
Evaporate and obtain nitrogen ligand containing active group；
（2）Prepare magnetic bidentate containing n-donor ligand：Under nitrogen protection, active group nitrogen ligand and magnetic Fe will be containedxOyNano particle
In being added sequentially to solvent I, it is stirred at reflux 8 ~ 36 hours under conditions of temperature is for 70 DEG C～150 DEG C, is cooled to room temperature, utilizes
Externally-applied magnetic field is separated after solvent I, is washed with toluene or ethanol 3～6 times, and then drying under reduced pressure, obtains magnetic bidentate containing n-donor ligand；
Wherein, solvent I is toluene or absolute ethyl alcohol, FexOyFor Fe2O3Or Fe3O4；
（3）Prepare the nitrogenous tin part of magnetic bidentate：Under nitrogen protection, by R2SnCl2With magnetic bidentate containing n-donor ligand according to mole
Than（0.8~1.8）：1 ratio is added in solvent II, is stirred at reflux 8 ~ 36 hours under conditions of temperature is for 50～80 DEG C,
Room temperature is cooled to, is separated after solvent II using externally-applied magnetic field, washed with ethanol 3 times, drying under reduced pressure, obtain final product the nitrogenous tin of magnetic bidentate
Ligand catalyst；Wherein solvent II be ethanol, propyl alcohol or butanol, R2SnCl2Middle R is CH3(CH2)m, m=0～5.
3. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterised in that：Institute
State step（1）The ratio of the amount of the material of middle silane coupler and alkyl diamine is 1～5：1, reaction temperature is 70 DEG C～150 DEG C,
Reaction time is 2～10 hours.
4. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 3, it is characterised in that：Institute
State step（1）The ratio of the amount of the material of middle silane coupler and alkyl diamine is 2：1, reaction temperature is 90 DEG C～100 DEG C, reaction
Time is 6～8 hours.
5. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterised in that：Institute
State step（1）Middle silane coupler is selected from vinyltrimethoxy silane, 3- r-chloropropyl trimethoxyl silanes, the second of 3- chloropropyls three
TMOS and 3- bromopropyl trimethoxy silanes, alkyl diamine is selected from 1,3 propane diamine, Isosorbide-5-Nitrae butanediamine and 1,5 pentanediamines.
6. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterised in that：Institute
State step（2）In nitrogen ligand containing active group and FexOyThe mol ratio of nano particle is（3～10）：1, nitrogen ligand containing active group
It is 1 with the mol ratio of solvent I：（120~180）.
7. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 6, it is characterised in that：Institute
State step（2）In nitrogen ligand containing active group and FexOyThe mol ratio of nano particle is 4：1, nitrogen ligand containing active group and solvent
I mol ratio is 1：140.
8. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterised in that：Institute
State step（2）The temperature conditionss of middle stirring are 100 DEG C, are stirred at reflux the time for 18h.
9. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterised in that：Institute
State step（3）Middle R2SnCl2It is 1.1 with the mol ratio of magnetic bidentate containing n-donor ligand：1.
10. the preparation method of the nitrogenous tin ligand catalyst of a kind of magnetic bidentate according to claim 2, it is characterised in that：
The step（3）The temperature conditionss of middle stirring are 70 DEG C, are stirred at reflux the time for 24h.
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| CN101757948A (en) * | 2010-01-29 | 2010-06-30 | 黑龙江省科学院石油化学研究院 | Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst |
| CN102489330A (en) * | 2011-11-28 | 2012-06-13 | 黑龙江省科学院石油化学研究院 | Preparation method of magnetic nitrogen-containing bidentate palladium ligand catalyst |
| CN102500418A (en) * | 2011-11-28 | 2012-06-20 | 黑龙江省科学院石油化学研究院 | Magnetic bidentate imide palladium ligand catalyst and preparation method thereof |
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| CN101757948A (en) * | 2010-01-29 | 2010-06-30 | 黑龙江省科学院石油化学研究院 | Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst |
| CN102489330A (en) * | 2011-11-28 | 2012-06-13 | 黑龙江省科学院石油化学研究院 | Preparation method of magnetic nitrogen-containing bidentate palladium ligand catalyst |
| CN102500418A (en) * | 2011-11-28 | 2012-06-20 | 黑龙江省科学院石油化学研究院 | Magnetic bidentate imide palladium ligand catalyst and preparation method thereof |
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