CN108929225A - A kind of methyl formylcaprylate isolation and purification method - Google Patents
A kind of methyl formylcaprylate isolation and purification method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
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Abstract
The invention discloses a kind of techniques that methyl formylcaprylate isolates and purifies, and first with mixed methyl aliphatic ester, the different of solubility stand still for crystals precipitation in low temperature environment in a solvent, then the initial gross separation of mixture is realized by filtering rapidly；Then light component and heavy constituent are collected using operating parameters such as multiple-grade molecular distillation technical controlling vapo(u)rizing temperature, vacuum degree, inlet amounies, to obtain the methyl formylcaprylate of high-purity.Simple process of the present invention, it is easy to operate, equipment investment and production cost are reduced, is easy to realize industrial production, economic benefits.
Description
Technical field
It is specially a kind of that the side for obtaining sterling is isolated and purified by methyl formylcaprylate crude product the present invention relates to oil and fat chemical field
Method.
Technical background
Methyl formylcaprylate also known as 9- oxo methyl pelargonate, are a kind of chemical intermediates with anticancer function, can be used for perfume (or spice)
The fields such as material, drug and plasticizer.Methyl formylcaprylate can occur addition reaction with the free radical of acryloyl diacid chloride and generate forefront
The amyl- 2- alkene -1- ketone of parathyrine synthetic 2- (6- methoxycarbonyl hexyl) ring；Can with 4- trimethyl silyl -3- butyne-1-ol into
Row addition reaction generates 13 carbon -9- alkene -12- ynoic acid methyl ester of 13- trimethyl silyl, this is a kind of effective anticancer drug
Ingredient；It can be further oxidized to the products such as azelaic acid hydrogen methyl esters, azelaic acid.In addition, it is a kind of common cosmetic additive agent,
There is very high application value in medicine and chemical field.But due to its thermal sensitivity height, separating-purifying difficulty is high, causes it in state
Price can not have always been high any more on interior and international market, reach 7200 yuan/gram.Therefore, the production separation and purifying of methyl formylcaprylate
Method has broad application prospects.
Currently, the common separation method in oil and fat chemical field has rectifying, UF membrane, urea adduct method, supercritical fluid extraction
Take with molecular distillation etc..For the physical property speciality of methyl formylcaprylate, all there is certain lack using these single separation methods
Point can only reach separating effect to a certain extent.Wherein, temperature is too low when rectifying is unable to reach separation requirement, and temperature is excessively high
It will lead to target product polymerization again；Membrane separation process is complicated for operation, and condition is harsh, and the preparation and cleaning of film can greatly increase separation
Cost；Urea adduct method is although at low cost, but can introduce new impurity and the rate of recovery is very low.Supercritical fluid extraction produces
Object is oxidizable, and stability is poor and high-tension apparatus cost investment is very big, is difficult to realize industrialization large-scale production.Therefore it needs to explore coupling
Close the method that several separation methods isolate and purify methyl formylcaprylate.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that methyl formylcaprylate isolates and purifies, to the effect that using freezing knot
The method that brilliant and multiple-grade molecular distillation is coupled, substep remove other compositions in methyl formylcaprylate crude product to obtain high-purity
Methyl formylcaprylate.
First with mixed methyl aliphatic ester, the different of solubility stand still for crystals precipitation in low temperature environment in a solvent, then
The initial gross separation of mixture is realized by filtering rapidly；Then using multiple-grade molecular distillation technical controlling vapo(u)rizing temperature, vacuum degree,
The operating parameters such as inlet amount collect light component and heavy constituent, to obtain the methyl formylcaprylate of high-purity.
To achieve the goals above, the present invention uses following scheme:
A kind of method that methyl formylcaprylate isolates and purifies, it is characterised in that: the method carries out in accordance with the following steps:
(1) methyl formylcaprylate crude product is uniformly mixed with organic solvent with volume ratio for 1:1~5, being placed in temperature is 0~15
DEG C cryogenic thermostat reactive bath technique in crystallize 1~5h after rapidly filter obtain filtrate A；The methyl formylcaprylate crude product is by oleic acid first
The product that ester cracks again through epoxidation；
(2) the filtrate A that step (1) obtains is placed in 1~60h of freezing and crystallizing in -30~15 DEG C of cryogenic thermostat reactive bath technique,
Then it is filtered rapidly at -20~10 DEG C and obtains liquor B, 0.5~2h of rotary evaporation takes off at 70~90 DEG C by the liquor B
Except solvent, mixed liquor crude product is obtained；
(3) the mixed liquor crude product obtained step (2) carries out first order molecular distillation, alternative condition be feed rate 0.5~
10g/min, 0.1~50Pa of vacuum degree, 30~80 DEG C of feeding temperature, 90~140 DEG C of vapo(u)rizing temperature, 100~300r/ of knifing rotating speed
Min obtains first order molecular distillation light component；
(4) the first order molecular distillation light component obtained step (3) carries out secondary molecules distillation, and alternative condition is charging speed
0.5~10g/min of rate, 0.1~50Pa of vacuum degree, 40~90 DEG C of feeding temperature, 100~220 DEG C of vapo(u)rizing temperature, knifing rotating speed
100~300r/min obtains secondary molecules distillation light component；
(5) by step (4) obtain secondary molecules distillation light component carry out three-level molecular distillation, select separation condition for into
Expect 0.5~10g/min of rate, 0.1~50Pa of vacuum degree, 40~90 DEG C of feeding temperature, 150~200 DEG C of vapo(u)rizing temperature, knifing turns
100~300r/min of speed, gained three-level molecular distillation light component, that is, target product methyl formylcaprylate.
Further, in step (1), the organic solvent is dehydrated alcohol, petroleum ether, n-hexane.
Further, in step (2), the freezing and crystallizing time is preferably 5h~30h more abundant to crystallize.
Further, in step (2), the rotary evaporation process goes the low-boiling-point substances such as water removal, solvent to avoid to subsequent point
The high vacuum of son distillation impacts, and preferably 80~90 DEG C of the rotating evaporation temperature.
Further, in step (3), the first order molecular distillation is preferably 0.5~5.0g/min of condition feed rate, very
0.1~10Pa of reciprocal of duty cycle, 50~70 DEG C of feeding temperature, 120~200 DEG C of vapo(u)rizing temperature, 200~300r/min of knifing rotating speed.
Further, in step (4), the secondary molecules distillation condition is preferably 0.5~5g/min of inlet amount, vacuum degree
0.1~10Pa, 70~90 DEG C of feeding temperature, 100~150 DEG C of vapo(u)rizing temperature, 200~300r/min of knifing rotating speed.
Further, in step (5), the excellent condition of three-level molecular distillation is selected as 0.5~5g/min of inlet amount, vacuum degree
0.1~10Pa, 70~90 DEG C of feeding temperature, 60~100 DEG C of vapo(u)rizing temperature, 200~300r/min of knifing rotating speed.
The preparation method of methyl formylcaprylate crude product of the present invention is specifically prepared in accordance with the following steps:
1) using methyl oleate as raw material, sequentially adding mass fraction is 30%~50% hydrogen peroxide, formic acid, is stirred at 60 DEG C
Reaction 8h is mixed, gained reaction mixture is washed with deionized water to neutrality, takes upper oil phase revolving to remove water, obtains epoxyoleic acid methyl esters
Crude product；The ratio between described amount of substance of methyl oleate, hydrogen peroxide, formic acid is 1:1.5:0.23；
2) the epoxyoleic acid first is measured according to the hydrochloric acid of GB/T1677-1981 plasticizer epoxide number-acetone measuring method
The epoxide number EMO of ester crude product；
3) tert-butyl alcohol, WO are sequentially added into the epoxyoleic acid methyl esters crude product3/ SBA-15 catalyst at 80 DEG C,
It is slowly added to the hydrogen peroxide that mass fraction is 30%~50%, fully reacting obtains methyl formylcaprylate crude product；The Epoxy oil
In terms of the additional amount of sour methyl esters crude product is come by the quality of the epoxide number, the quality of the epoxide number is epoxy described in epoxide number *
Methyl oleate molal weight；The epoxide number and the tert-butyl alcohol, WO3The mass ratio of/SBA-15 catalyst is 1:2:25；Described is double
The amount of the substance of oxygen water is calculated as 0.769mol*100g/mol with the epoxide number.
The mass percentage of each component is as follows in products therefrom methyl formylcaprylate crude product warp: methyl formylcaprylate 10%~
30%, aldehyde C-9 10%~23%, methyl oleate 12%~30%, epoxyoleic acid methyl esters 1%~15%, 9,10- dihydroxy are stearic
The high-boiling components such as sour methyl esters 10%~20%, other 10%~20%.
Wherein, the catalyst WO3/ SBA-15 is specifically prepared in accordance with the following steps:
1. using mass fraction to pre-process for the hydrogen peroxide of 10-35% in SBA-15 molecular sieve, it is washed out simultaneously
It is dried for standby；
2. by pretreated SBA-15 molecular sieve and WO3It is added in toluene, N2It is stirred under atmosphere for 24 hours, solution colour is by depth
Solid is obtained by filtration after becoming light blue in blue, and obtained solid product is roasted at 550 DEG C and obtains pale yellow colored solid body catalyst
WO3/SBA-15；The SBA-15 molecular sieve and WO3Mass ratio be 1:0.05；The additional amount of the toluene is with described
The quality of SBA-15 molecular sieve is calculated as 8ml/g.
Compared with prior art, the beneficial effects of the present invention are:
The present invention isolates and purifies the method coupling freezing and crystallizing and multiple-grade molecular distillation separation method of methyl formylcaprylate, freezing
Crystallization stage adds organic solvent as the formation of methyl esters nucleus and provides stable environment.Make crystallization time with the method for winterization
Elongated crystallization is more abundant, and is easily removed using low-boiling nontoxic solvent and do not introduce new impurity.Molecular distillation stage, Gao Zhen
It is heated to make material for distillation under reciprocal of duty cycle, and process is short, and the time significantly shortens, and high-thermosensitive substance methyl formylcaprylate is not susceptible to gather
It closes.Multiple-grade molecular distillation specific aim separation impurity improves the rate of recovery of product, and can be in time according to upper level product tune
Whole distillation parameter.Method of the present invention is simple, easy to operate, reduces equipment investment and production cost, easily realizes industry
Metaplasia produces, economic benefits.
Detailed description of the invention
Fig. 1 freezing and crystallizing and molecular distillation integrated separation purify methyl formylcaprylate method flow diagram.
Specific embodiment
Below in conjunction with preferred embodiment, the present invention is described further.Following embodiment is descriptive, rather than
Limit the present invention.
Catalyst WO as described in the examples3/ SBA-15's the preparation method comprises the following steps: uses 30% for 10gSBA-15 molecular sieve
Hydrogen peroxide handled, washed and is dried for standby, then take 0.5gWO3, it is dissolved in 80ml toluene, N2It is stirred in atmosphere
24h.After solution becomes light blue from navy blue, suction filtration obtains solid.Toluene washs three times repeatedly, is dried at 100 DEG C,
5h is finally roasted at 550 DEG C obtains pale yellow colored solid body catalyst.
Embodiment 1
1) 85% methyl oleate 100g, 30% hydrogen peroxide 20.64g, formic acid 2.18g are weighed and sequentially adds three-necked flask, is controlled
Temperature 60 C processed is stirred to react 8h, and deionized water is washed till neutrality, takes upper oil phase, and revolving removes water, obtains 80.24g epoxyoleic acid
Methyl esters crude product；
2) thick according to the measurement of GB/T1677-1981 plasticizer epoxide number (hydrochloric acid-acetone method) measurement epoxyoleic acid methyl esters
The epoxide number EMO of product is 4.17；
3) tert-butyl alcohol 16.04g, WO are weighed3/ SBA-15 catalyst 1.60g, sequentially adds three-necked flask, is slowly added dropwise
30% hydrogen peroxide 15.13g, reacts 20min after completion of dropwise addition, 90 DEG C of revolving 1h obtain methyl formylcaprylate crude product.
One methyl formylcaprylate crude product of table composition
It accurately weighs 100g methyl formylcaprylate crude product and 500g dehydrated alcohol stirs 5h at normal temperature and obtains mixed solution.
(1) mixed liquor sealing is all placed in cryogenic thermostat reactive bath technique, 10 DEG C of set temperature, crystallizes 5h, quickly filters
Obtain filtrate A1；
(2) filtrate A1 is again sealed off and is all placed in cryogenic thermostat reactive bath technique, extremely -30 DEG C of slow cooling, the retention time
5h.To be crystallized abundant, rapid filtration under suction obtains liquor B 1；
(3) liquor B 1 is rotated to 2h removal etoh solvent at 80 DEG C；
(4) control feed rate is 0.7g/min, and knifing rotating speed 250r/min, feeding temperature is 50 DEG C, and vapo(u)rizing temperature is
120 DEG C, observe that heavy constituent receiving flask has faint yellow oil droplet to drip, condenser pipe has oil droplet condensation, and hair dryer is used in end to be distilled
Condenser pipe oil droplet heating nature is instilled into light component receiving flask and obtains first order molecular distillation light component；
(5) liquid that first order molecular distillation light component receiving flask receives in step (4) is subjected to the second level as raw material
Molecular distillation, control distillation condition is feed rate 0.7g/min, 90 DEG C of feeding temperature, 100 DEG C of vapo(u)rizing temperature, and knifing rotating speed
250r/min obtains secondary molecules distillation light component；
(6) liquid that secondary molecules distillation light component receiving bottle receives in step (5) is subjected to the third level as raw material
Molecular distillation, control condition are feed rate 1.0g/min, knifing rotating speed 250r/min, and feeding temperature is 70 DEG C, distillation temperature
Degree is 60 DEG C, and obtaining three-level molecular distillation light component is methyl formylcaprylate sterling；
It detects methyl formylcaprylate content and rises to 82.5% from 16.7%, the rate of recovery 33.2%.
Embodiment 2
1) 85% methyl oleate 500g, 50% hydrogen peroxide 103.20g, formic acid 10.90g are weighed and sequentially adds three-necked flask,
Control temperature 60 C is stirred to react 8h, and deionized water is washed till neutrality and takes upper oil phase, and revolving removes water.Obtain 450.23g Epoxy oil
Sour methyl esters crude product；
2) thick according to the measurement of GB/T1677-1981 plasticizer epoxide number (hydrochloric acid-acetone method) measurement epoxyoleic acid methyl esters
The epoxide number EMO4.30 of product；
3) tert-butyl alcohol 187g, WO are weighed3/ SBA-15 catalyst 15g.Three-necked flask is sequentially added, is slowly added dropwise 30% pair
Oxygen water 176g, reacts 20min after completion of dropwise addition, 90 DEG C of revolving 2h obtain methyl formylcaprylate crude product.
Two methyl formylcaprylate crude product of table composition
(1) accurately weigh 100g methyl formylcaprylate crude product under the miscible room temperature of 100g n-hexane stir 1h obtain mixing it is molten
Liquid；
(2) mixed liquor sealing is all placed in cryogenic thermostat reactive bath technique, 0 DEG C of set temperature, crystallizes 5h, quickly filters to take
Filtrate A2；
(3) sealing of filtrate A2 obtained by step 2) is all placed in cryogenic thermostat reactive bath technique, slow cooling is protected to -10 DEG C
Time 30h is held, to be crystallized abundant, rapid filtration under suction obtains liquor B 2；
(4) liquor B 2 obtained by step (3) is rotated into 1h removal solvent hexane at 90 DEG C；
(5) control feed rate is 5g/min, and knifing rotating speed 300r/min, feeding temperature is 60 DEG C, vapo(u)rizing temperature 140
DEG C, observe that heavy constituent receiving flask has faint yellow oil droplet to drip, condenser pipe has oil droplet condensation.End hair dryer to be distilled will be cold
Solidifying pipe oil droplet heating nature instills light component receiving flask and obtains first order molecular distillation light component；
(6) liquid that the distillation light component receiving flask of first order molecular obtained by step (5) receives is carried out second as raw material
Grade molecular distillation, control distillation condition is feed rate 10g/min, 90 DEG C of feeding temperature, 140 DEG C of vapo(u)rizing temperature, and knifing rotating speed
300r/min obtains secondary molecules distillation light component；
(7) liquid that the intermediate molecular distillation light component receiving bottle of step (6) receives is subjected to third fraction as raw material
Son distillation, control condition is inlet amount 1.0g/min, knifing rotating speed 250r/min, and feeding temperature is 80 DEG C, and vapo(u)rizing temperature is
90 DEG C, obtaining three-stage distillation light component is methyl formylcaprylate sterling；
8) detection methyl formylcaprylate content rises to 87.5% from 23.3%, the rate of recovery 35.2%.
Embodiment 3
1) 85% methyl oleate 500g, 30% hydrogen peroxide 61.92g, formic acid 10.90g are weighed and sequentially adds three-necked flask；Control
Temperature 60 C processed is stirred to react 8h；Deionized water is washed till neutrality, takes upper oil phase revolving to remove water, obtains 405.8g mixture；
2) thick according to the measurement of GB/T1677-1981 plasticizer epoxide number (hydrochloric acid-acetone method) measurement epoxyoleic acid methyl esters
The epoxide number EMO5.8 of product；
3) tert-butyl alcohol 200.16g, WO are weighed3/ SBA-15 catalyst 16.2g, sequentially adds three-necked flask, is slowly added dropwise
50% hydrogen peroxide 114g reacts 20min to fully reacting and obtains methyl formylcaprylate crude product after completion of dropwise addition.
Three methyl formylcaprylate crude product of table composition
(1) accurately weigh 100g methyl formylcaprylate crude product under the miscible room temperature of 300g petroleum ether stir 1h obtain mixing it is molten
Liquid；
(2) mixed liquor sealing is all placed in cryogenic thermostat reactive bath technique, 15 DEG C of set temperature, crystallizes 30h, quickly filters
Take filtrate A3；
(3) sealing of filtrate A3 obtained by step (2) is all placed in cryogenic thermostat reactive bath technique, slow cooling is protected to -10 DEG C
Time 5h is held, to be crystallized abundant, rapid filtration under suction obtains liquor B 3；
(4) liquor B 3 obtained by step (3) is rotated into 1h removal solvent petroleum ether at 90 DEG C；
(5) control feed rate is 5.2g/min, and knifing rotating speed 300r/min, feeding temperature is 60 DEG C, and vapo(u)rizing temperature is
120 DEG C, observe that heavy constituent receiving flask has faint yellow oil droplet to drip, condenser pipe has oil droplet condensation.Hair dryer is used in end to be distilled
Condenser pipe oil droplet heating nature is instilled into light component receiving flask and obtains first order molecular distillation light component；
(6) liquid that the distillation light component receiving flask of first order molecular obtained by step (5) receives is carried out second as raw material
Grade molecular distillation, control distillation condition is feed rate 5.2g/min, and 90 DEG C of feeding temperature, 150 DEG C of vapo(u)rizing temperature, knifing turns
Fast 100r/min obtains secondary molecules distillation light component；
(7) liquid that the intermediate molecular distillation light component receiving bottle of step (6) receives is subjected to third fraction as raw material
Son distillation, control condition is inlet amount 1.0g/min, knifing rotating speed 250r/min, and feeding temperature is 80 DEG C, and vapo(u)rizing temperature is
100 DEG C, obtaining three-stage distillation light component is methyl formylcaprylate sterling；
It detects methyl formylcaprylate content and rises to 88.9% from 19.4%, the rate of recovery 35.2%.
Claims (8)
1. a kind of method that methyl formylcaprylate isolates and purifies, it is characterised in that: the method carries out in accordance with the following steps:
(1) methyl formylcaprylate crude product is uniformly mixed with organic solvent with volume ratio for 1:1~5, being placed in temperature is 0~15 DEG C
Acquisition filtrate A is filtered rapidly after crystallizing 1~5h in cryogenic thermostat reactive bath technique；The methyl formylcaprylate crude product is passed through by methyl oleate
The product that epoxidation cracks again；
(2) the filtrate A that step (1) obtains is placed in 1~60h of freezing and crystallizing in -30~15 DEG C of cryogenic thermostat reactive bath technique, then
It is filtered rapidly at -20~10 DEG C and obtains liquor B, 0.5~2h of rotary evaporation removing is molten at 70~90 DEG C by the liquor B
Agent obtains mixed liquor crude product；
(3) the mixed liquor crude product for obtaining step (2) carries out first order molecular distillation, and alternative condition is 0.5~10g/ of feed rate
Min, 0.1~50Pa of vacuum degree, 30~80 DEG C of feeding temperature, 90~140 DEG C of vapo(u)rizing temperature, 100~300r/min of knifing rotating speed,
Obtain first order molecular distillation light component；
(4) the first order molecular distillation light component obtained step (3) carries out secondary molecules distillation, and alternative condition is feed rate
0.5~10g/min, 0.1~50Pa of vacuum degree, 40~90 DEG C of feeding temperature, 100~220 DEG C of vapo(u)rizing temperature, knifing rotating speed 100
~300r/min obtains secondary molecules distillation light component；
(5) the secondary molecules distillation light component obtained step (4) carries out three-level molecular distillation, selects separation condition for charging speed
0.5~10g/min of rate, 0.1~50Pa of vacuum degree, 40~90 DEG C of feeding temperature, 150~200 DEG C of vapo(u)rizing temperature, knifing rotating speed
100~300r/min, gained three-level molecular distillation light component, that is, target product methyl formylcaprylate.
2. the method as described in claim 1, it is characterised in that: in step (1), the organic solvent is dehydrated alcohol, stone
Oily ether, n-hexane, tetrahydrofuran and ethyl acetate.
3. the method as described in claim 1, it is characterised in that: in step (2), the freezing and crystallizing time is 5h~30h.
4. the method as described in claim 1, it is characterised in that: in step (2), the rotating evaporation temperature is 80~90
℃。
5. the method as described in claim 1, it is characterised in that: in step (3), the first order molecular distillation condition are as follows: into
Expect 0.5~5.0g/min of rate, 0.1~10Pa of vacuum degree, 50~70 DEG C of feeding temperature, 120~200 DEG C of vapo(u)rizing temperature, knifing
200~300r/min of revolving speed.
6. the method as described in claim 1, it is characterised in that: in step (4), the secondary molecules distillation condition is charging
Measure 0.5~5g/min, 0.1~10Pa of vacuum degree, 70~90 DEG C of feeding temperature, 100~150 DEG C of vapo(u)rizing temperature, knifing rotating speed 200
~300r/min.
7. the method as described in claim 1, it is characterised in that: in step (5), the three-level molecular distillation condition is charging
Measure 0.5~5g/min, 0.1~10Pa of vacuum degree, 70~90 DEG C of feeding temperature, 60~100 DEG C of vapo(u)rizing temperature, knifing rotating speed 200
~300r/min.
8. the method as described in claim 1, it is characterised in that: the methyl formylcaprylate crude product is specifically in accordance with the following steps
It is prepared:
1) using methyl oleate as raw material, sequentially adding mass fraction is 30%~50% hydrogen peroxide, formic acid, is stirred at 60 DEG C anti-
8h is answered, gained reaction mixture is washed with deionized water to neutrality, takes upper oil phase revolving to remove water, it is thick to obtain epoxyoleic acid methyl esters
Product；The ratio between described amount of substance of methyl oleate, hydrogen peroxide, formic acid is 1:1.5:0.23；
2) thick according to the hydrochloric acid of GB/T1677-1981 plasticizer epoxide number-acetone measuring method measurement epoxyoleic acid methyl esters
The epoxide number EMO of product；
3) tert-butyl alcohol, WO are sequentially added into the epoxyoleic acid methyl esters crude product3/ SBA-15 catalyst slowly adds at 80 DEG C
Enter the hydrogen peroxide that mass fraction is 30%~50%, fully reacting obtains methyl formylcaprylate crude product；The epoxyoleic acid methyl esters
In terms of the additional amount of crude product is come by the quality of the epoxide number, the quality of the epoxide number is epoxyoleic acid first described in epoxide number *
Ester molal weight；The epoxide number and the tert-butyl alcohol, WO3The mass ratio of/SBA-15 catalyst is 1:2:25；The hydrogen peroxide
The amount of substance is calculated as 0.769mol*100g/mol with the epoxide number.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810704125.0A CN108929225B (en) | 2018-06-30 | 2018-06-30 | Methyl pelargonate separating and purifying method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810704125.0A CN108929225B (en) | 2018-06-30 | 2018-06-30 | Methyl pelargonate separating and purifying method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112209964A (en) * | 2020-10-20 | 2021-01-12 | 浙江万盛股份有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN114874070A (en) * | 2022-05-30 | 2022-08-09 | 南京威尔药业科技有限公司 | Preparation method of high-purity hexadecanol and octadecanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351697A (en) * | 2011-11-08 | 2012-02-15 | 杭州友邦香料香精有限公司 | Preparation method of methyl formylcaprylate |
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| CN102351697A (en) * | 2011-11-08 | 2012-02-15 | 杭州友邦香料香精有限公司 | Preparation method of methyl formylcaprylate |
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| 马利娜: "油酸甲酯提纯及氧化裂解制醛", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112209964A (en) * | 2020-10-20 | 2021-01-12 | 浙江万盛股份有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN112209964B (en) * | 2020-10-20 | 2023-04-07 | 浙江万盛股份有限公司 | Preparation method of TCPP (trichloropropylphosphate) flame retardant |
| CN114874070A (en) * | 2022-05-30 | 2022-08-09 | 南京威尔药业科技有限公司 | Preparation method of high-purity hexadecanol and octadecanol |
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