CN102079702B - Preparation method of monobutyl itaconate - Google Patents
Preparation method of monobutyl itaconate Download PDFInfo
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Abstract
The invention discloses a preparation method of monobutyl itaconate, which comprises the following steps: under normal pressure, adding catalyst, polymerization inhibitor and dehydrating agent into itaconic acid and n-butyl alcohol, which are used as raw materials, to carry out esterification reaction; after the esterification reaction finishes, adding water into the reaction product system; carrying out extraction, collecting the organic phase, and carrying out vacuum dehydration on the organic phase to obtain a crude product; and crystallizing the crude product at low temperature, and centrifugalizing to obtain a crystal which is the required monobutyl itaconate. The preparation method of monobutyl itaconate is implemented by optimizing various parameters in the reaction and matching various processing schemes after the reaction finishes. The monobutyl itaconate prepared by the method has the advantages of high yield (up to 60-75%) and high purity (higher than 97%); and the preparation method has the advantages of simple technological process and low cost, and is suitable for industrial production.
Description
Technical field
The present invention relates to the preparation of monoesters, be specifically related to a kind of preparation method of methylene-succinic acid mono.
Background technology
In chemical industry, a kind of comparatively general method that generates ester is exactly in the presence of an acidic catalyst, and carboxylic acid and alkyl alcohol carry out esterification, make corresponding carboxylic acid ester product.Because esterification is a kind of typical reversible reaction,, must strengthens proportioning raw materials or in time remove the water that dereaction generates in order to improve the transformation efficiency of reaction.
Diprotic acid is used to make the method for monoesters at present, and it is few that documents and materials are reported.It is esterification too that diprotic acid generates monoesters with the alcohol reaction, and key component is control dibasic acid esters content.The control of the control of the control of proportioning, temperature of reaction, catalysts and in reaction process just in the purification of subsequent handling.Temperature is high more generally speaking, and speed of reaction is fast more, and the reaction times is short more.But temperature of reaction is high, and side reaction is also just many more.
The manufacturing of existing methylene-succinic acid mono is a raw material with methylene-succinic acid and propyl carbinol normally, under the effect of catalyzer, makes methylene-succinic acid and propyl carbinol esterification slough an one's share of expenses for a joint undertaking water and prepares, and its principal reaction equation is following:
Because methylene-succinic acid itself has the C=C unsaturated double-bond; Under strongly acidic catalyst and hot conditions, be easy to take place polymerization side reactions; Influence reaction yield and make troubles for follow-up purification process; Think the yield that improves product, be not the superfluous The more the better problem of the high more good more or reaction mass of the selection of temperature, but the selective problems of the course end that reacts.
Reaction end is too early, must cause unreacted methylene-succinic acid too much, and reaction end is slow excessively, must have the by product dibutyl itaconate and produce with some polymkeric substance, and these production of by-products strengthen difficulty for follow-up purification process.
At present, utilize methylene-succinic acid and propyl carbinol suitability for industrialized production methylene-succinic acid mono, its productive rate is very low and products obtained therefrom purity is also very low, and therefore developing highly purified methylene-succinic acid mono has very important practical value.
Summary of the invention
The objective of the invention is to the deficiency to prior art, provide that a kind of productive rate is high, product purity is high, technology is simple, cost is low, and can realize the preparation method of the methylene-succinic acid mono of suitability for industrialized production.
Above-mentioned purpose of the present invention is achieved through following scheme:
A kind of preparation method of methylene-succinic acid mono, this method are under condition of normal pressure, are raw material with methylene-succinic acid and propyl carbinol; Esterification takes place in simultaneously in addition suitable reaction promoter at a certain temperature, finishes esterification after reaction for some time; In the reaction product system, add entry, after washing and extraction treatment, collect organic phase; After this organic phase carried out vacuum hydro-extraction and handle; The thick product of gained is handled through low temperature crystallization again, and the gained xln is finished product after the spinning, just required methylene-succinic acid mono.
Among the preparation method of above-mentioned methylene-succinic acid mono; The selection in optimization, esterification reaction temperature and the reaction times of the consumption selection of reaction raw materials, the selection of reaction promoter and consumption thereof, the subsequent disposal of reaction product etc., all productive rate and the purity to product of the present invention has very big influence, therefore; The inventor has carried out after lot of test gropes these factors; Obtain following data, adopt the following data of optimizing, can obtain the highly purified methylene-succinic acid mono of high yield.
Among the preparation method of above-mentioned methylene-succinic acid mono, the mol ratio of methylene-succinic acid and propyl carbinol is 1: (0.9～1.3).
Among the preparation method of above-mentioned methylene-succinic acid mono, said suitable reaction promoter is meant catalyzer, stopper and band aqua, wherein:
Catalyzer adopts tosic acid, sodium-acetate or sodium pyrosulfate, and catalyst consumption is 0.1～0.2% of total inventory, and said total inventory is meant the total mass of methylene-succinic acid, propyl carbinol, catalyzer, stopper and these five kinds of materials of band aqua before the reaction;
Stopper adopts MEHQ, Resorcinol or phenothiazine, and its consumption is 0.05～0.2% of total inventory, and preferred 0.05～0.1%;
The effect of band aqua is band water and control reaction temperature, and the band aqua can adopt sherwood oil, hexanaphthene or toluene, and its consumption is 10～20% of total inventory, preferred hexanaphthene.
Among the preparation method of above-mentioned methylene-succinic acid mono, the temperature of esterification is 80～130 ℃, preferred 90～120 ℃.
Among the preparation method of above-mentioned methylene-succinic acid mono, the time of esterification is 4～8 hours, preferred 5～7 hours.
Among the preparation method of above-mentioned methylene-succinic acid mono, esterification adds entry after finishing in the reaction product system, leave standstill extraction after the stirring, collects organic phase, through the water extraction unreacted methylene-succinic acid in the reaction product system is removed.
Among the preparation method of above-mentioned methylene-succinic acid mono, above-mentioned organic phase of collecting through water extraction back is carried out vacuum hydro-extraction handle, handle through vacuum hydro-extraction and can remove band aqua and the unreacted propyl carbinol in the reaction product system.
Among the preparation method of above-mentioned methylene-succinic acid mono; Vacuum hydro-extraction is handled and to be contained dibutyl itaconate, partially polymerized itaconic ester in the thick product of back gained and not distill butanols completely, and at this moment, the inventor utilizes the physicochemical property of methylene-succinic acid mono; Methylene-succinic acid mono crystallization under the low temperature; And other mixtures are non-crystallizable, the aforementioned crude product is carried out low temperature crystallization handle, and required methylene-succinic acid mono is separated from the mixed system of reaction product; Tc adopts 7～16 ℃, preferred 10～12 ℃.Handle through low temperature crystallization, the methylene-succinic acid mono has been a crystal, and dibutyl itaconate or liquid only need carry out centrifugal treating with solid-liquid separation again, can obtain required methylene-succinic acid mono.
Among the preparation method of above-mentioned methylene-succinic acid mono, its yield of methylene-succinic acid mono that finally obtains is very high, can be up to 60～75%, and also purity is also very high, can reach more than 97%.
Among the preparation method of above-mentioned methylene-succinic acid mono; Inevitably can produce dibutyl itaconate more or less; This dibutyl itaconate can prepare dibutyl itaconate content and reach the dibutyl itaconate product more than 98% through handling, and sells as sub product.
Among the preparation method of above-mentioned methylene-succinic acid mono; In crystallisation process, there is the methylene-succinic acid mono of part not separate out; Remain in the crystallized liquid; Crystallized liquid is handled further, can the methylene-succinic acid mono that not crystallize out be converted into dibutyl itaconate, sell as the accessory substance dibutyl itaconate.
Compared with prior art, the present invention has following beneficial effect:
The present invention passes through various Parameter Optimization in the reaction, and the collocation of the various processing schemes in reaction end back, finally obtains a kind of preparation method of methylene-succinic acid mono; Not only yield is high to adopt the methylene-succinic acid mono of this method preparation, can be up to 60～75%, and also purity is also very high; Can reach more than 97%, in addition, this preparing method's technological process is simple; With low cost, and be fit to very much suitability for industrialized production.
Embodiment
The present invention relates to a kind of preparation method of methylene-succinic acid mono, this method is under condition of normal pressure, is raw material with methylene-succinic acid and propyl carbinol; Esterification takes place in simultaneously in addition suitable reaction promoter at a certain temperature, finishes esterification after reaction for some time; In the reaction product system, add entry, after washing and extraction treatment, collect organic phase; After this organic phase carried out vacuum hydro-extraction and handle; The thick product of gained is handled through low temperature crystallization again, and the gained xln is finished product after the spinning, just required methylene-succinic acid mono.
Among the preparation method of above-mentioned methylene-succinic acid mono; The selection in optimization, esterification reaction temperature and the reaction times of the consumption selection of reaction raw materials, the selection of reaction promoter and consumption thereof, the subsequent disposal of reaction product etc., all productive rate and the purity to product of the present invention has very big influence, therefore; The inventor has carried out after lot of test gropes these factors; Obtain following data, adopt the following data of optimizing, can obtain the highly purified methylene-succinic acid mono of high yield.
Wherein, the mol ratio of methylene-succinic acid and propyl carbinol is 1: (0.9～1.3), the reaction promoter of employing are catalyzer, stopper and band aqua.
Said catalyzer adopts tosic acid, sodium-acetate or sodium pyrosulfate; Catalyst consumption is 0.1～0.2% of total inventory, and said total inventory is meant the total mass of methylene-succinic acid, propyl carbinol, catalyzer, stopper and these five kinds of materials of band aqua before the reaction; Stopper adopts MEHQ, Resorcinol or phenothiazine, and its consumption is 0.05～0.2% of total inventory, and preferred 0.05～0.1%; The effect of band aqua is band water and control reaction temperature, and the band aqua can adopt sherwood oil, hexanaphthene or toluene, and its consumption is 10～20% of total inventory, preferred hexanaphthene.
Among the preparation method of above-mentioned methylene-succinic acid mono, the temperature of esterification is 80～130 ℃, preferred 90～120 ℃.The time of esterification is 4～8 hours, preferred 5～7 hours.And esterification adds entry after finishing in the reaction product system, leave standstill extraction after the stirring, collects organic phase, through the water extraction unreacted methylene-succinic acid in the reaction product system is removed.
Above-mentioned organic phase of collecting through water extraction back is carried out vacuum hydro-extraction handle, handle through vacuum hydro-extraction and can remove band aqua and the unreacted propyl carbinol in the reaction product system.Vacuum hydro-extraction is handled and to be contained dibutyl itaconate, partially polymerized itaconic ester in the thick product of back gained and not distill butanols completely, and at this moment, the inventor utilizes the physicochemical property of methylene-succinic acid mono; Methylene-succinic acid mono crystallization under the low temperature; And other mixtures are non-crystallizable, the aforementioned crude product is carried out low temperature crystallization handle, and required methylene-succinic acid mono is separated from the mixed system of reaction product; Tc adopts 7～16 ℃, preferred 10～12 ℃.Handle through low temperature crystallization, the methylene-succinic acid mono has been a crystal, and dibutyl itaconate or liquid only need carry out centrifugal treating with solid-liquid separation again, can obtain required methylene-succinic acid mono.
Below in conjunction with specific embodiment the present invention is done description further, but specific embodiment is not done any qualification to the present invention.
Embodiment 1
The methylene-succinic acid mono of present embodiment, its preparation method comprises the steps:
Step 1. is in the four-hole boiling flask that whipping appts, TM, water trap and condensing surface are housed; The propyl carbinol of the methylene-succinic acid of adding 150g (1.15mol), 0.5g catalyzer (tosic acid), 0.25g stopper (MEHQ), 85.3g (1.15mol) and 50g band aqua (hexanaphthene); Esterification is carried out in heating while stirring; Reaction solution began to reflux and have moisture content to take out of, 80～110 ℃ of back flow reaction of temperature 4～5 hours;
After step 2. esterification finishes; Band aqua hexanaphthene is sloughed in insulation, cools to 60 ℃, adds the stirring of 300g pure water and is warming up to 60 ℃; Restir 30 minutes; Be transferred to extraction flask extraction (water is extraction agent), collect lower floor's sample (organic phase), lower floor's sample dewaters down at 80 ℃ through vacuum and obtains the thick product of little yellow transparent;
Step 3. is handled the thick product of step 2 preparation gained at 7 ℃ of low temperature crystallizations, centrifugal collection xln 139.4g, and this xln is finished product, the required methylene-succinic acid mono of present embodiment just, yield is 65.1%, product purity 98.20%.
Embodiment 2
The methylene-succinic acid mono of present embodiment, its preparation method comprises the steps:
Step 1. adds the methylene-succinic acid of 150g (1.15mol), 0.5g catalyzer (sodium-acetate) in the four-hole boiling flask that whipping appts, TM, water trap and condensing surface are housed; 0.25g stopper (Resorcinol); 85.3g propyl carbinol (1.15mol), 50g is with aqua (toluene), and esterification is carried out in heating while stirring; Reaction solution began to reflux and have moisture content to take out of, 110～140 ℃ of back flow reaction of temperature 4～6 hours;
After step 2. esterification finished, band aqua toluene was sloughed in insulation, cools to 60 ℃, added the stirring of 300g pure water and was warming up to 60 ℃, and restir 30 minutes is transferred to extraction flask extraction (water is extraction agent), collects lower floor's sample (organic phase); Lower floor's sample obtains faint yellow transparent thick product through vacuum hydro-extraction again;
Step 3. through 10 ℃ of freezing and crystallizings, centrifugally obtains the thick product of step 2 preparation gained pure article and is methylene-succinic acid mono 143.2g, and yield is 66.7%, product purity 97.80%.
Embodiment 3
The methylene-succinic acid mono of present embodiment, its preparation method comprises the steps:
Step 1. adds the methylene-succinic acid of 150g (1.15mol), 0.5g catalyst sulfuric acid hydrogen sodium in the four-hole boiling flask that whipping appts, TM, water trap and condensing surface are housed; 0.25g stopper MEHQ; 93.8g propyl carbinol (1.265mol), the 50g hexanaphthene, esterification is carried out in heating while stirring; Reaction solution began to reflux and have moisture content to take out of, 90～110 ℃ of back flow reaction of temperature 5～6 hours;
After step 2. esterification finished, band aqua hexanaphthene was sloughed in insulation, cools to 60 ℃, added the stirring of 300g pure water and was warming up to 60 ℃, and restir 30 minutes is transferred to extraction flask extraction (water is extraction agent), collects lower floor's sample (organic phase); Lower floor's sample obtains faint yellow transparent thick product through vacuum hydro-extraction again;
Step 3. through 12 ℃ of crystallizations, centrifugally obtains the thick product of step 2 preparation gained pure article and is methylene-succinic acid mono 158.4g, and yield is 73.8%, product purity 98.10%.
Embodiment 4
The methylene-succinic acid mono of present embodiment, its preparation method comprises the steps:
Step 1. adds the methylene-succinic acid of 150g (1.15mol), 0.5g catalyzer tosic acid in the four-hole boiling flask that whipping appts, TM, water trap and condensing surface are housed; 0.25g stopper MEHQ; 93.8g propyl carbinol (1.265mol), the 50g sherwood oil, esterification is carried out in heating while stirring; Reaction solution began to reflux and have moisture content to take out of, 90～110 ℃ of back flow reaction of temperature 3～4 hours;
After step 2. esterification finished, band aqua sherwood oil was sloughed in insulation, cools to 60 ℃, added the stirring of 300g pure water and was warming up to 60 ℃, restir 30 minutes.Be transferred to extraction flask extraction (water is extraction agent), collect lower floor's sample (organic phase); Lower floor's sample obtains faint yellow transparent thick product through vacuum hydro-extraction again;
Step 3. through crystallization under 11 ℃ of low temperature, centrifugally obtains the thick product of step 2 preparation gained pure article and is methylene-succinic acid mono 160.0g, and yield is 74.5%, product purity 98.30%.
Embodiment 5
The methylene-succinic acid mono of present embodiment, its preparation method comprises the steps:
Step 1. adds the methylene-succinic acid of 150g (1.15mol), 0.5g catalyzer tosic acid in the four-hole boiling flask that whipping appts, TM, water trap and condensing surface are housed; 0.25g stopper thiodiphenylamine; 96.3g propyl carbinol (1.3mol), the 30g hexanaphthene, esterification is carried out in heating while stirring; Reaction solution began to reflux and have moisture content to take out of, 90～130 ℃ of back flow reaction of temperature 3～4 hours;
After step 2. esterification finished, band aqua hexanaphthene was sloughed in insulation, cools to 60 ℃, added the stirring of 300g pure water and was warming up to 60 ℃, and restir 30 minutes is transferred to extraction flask extraction (water is extraction agent), collects lower floor's sample (organic phase); Lower floor's sample obtains faint yellow transparent thick product through vacuum hydro-extraction again;
Step 3. through 8 ℃ of low temperature crystallizations, centrifugally obtains the thick product of step 2 preparation gained pure article and is methylene-succinic acid mono 154.4g, and yield is 72.2%, product purity 98.60%.
Embodiment 6
The methylene-succinic acid mono of present embodiment, its preparation method comprises the steps:
Step 1. adds the methylene-succinic acid of 150g (1.15mol), 0.5g catalyzer tosic acid in the four-hole boiling flask that whipping appts, TM, water trap and condensing surface are housed; 0.25g stopper MEHQ; 96.3g propyl carbinol (1.3mol), the 50g hexanaphthene, esterification is carried out in heating while stirring; Reaction solution began to reflux and have moisture content to take out of, 90～120 ℃ of back flow reaction of temperature 3～4 hours;
After step 2. esterification finished, band aqua hexanaphthene was sloughed in insulation, cools to 60 ℃, added the stirring of 300g pure water and was warming up to 60 ℃, and restir 30 minutes is transferred to extraction flask extraction (water is extraction agent), collects lower floor's sample (organic phase); Lower floor's sample obtains faint yellow transparent thick product through vacuum hydro-extraction again;
Step 3. through 13 ℃ of low temperature crystallizations, centrifugally obtains the thick product of step 2 preparation gained pure article and is methylene-succinic acid mono 155.6g, and yield is 72.5%, product purity 97.60%.
Embodiment 7
The methylene-succinic acid mono of present embodiment, its preparation method comprises the steps:
Step 1. adds the methylene-succinic acid of 150g (1.15mol), 0.5g catalyzer tosic acid in the four-hole boiling flask that whipping appts, TM, water trap and condensing surface are housed; 0.25g stopper MEHQ; 107.5g propyl carbinol (1.45mol), the 80g hexanaphthene, esterification is carried out in heating while stirring; Reaction solution began to reflux and have moisture content to take out of, 90～110 ℃ of back flow reaction of temperature 4～5 hours;
After step 2. esterification finished, band aqua hexanaphthene was sloughed in insulation, cools to 60 ℃, added the stirring of 300g pure water and was warming up to 60 ℃, and restir 30 minutes is transferred to extraction flask extraction (water is extraction agent), collects lower floor's sample (organic phase); Lower floor's sample obtains faint yellow transparent thick product through vacuum hydro-extraction again;
Step 3. through 16 ℃ of low temperature crystallizations, centrifugally obtains the thick product of step 2 preparation gained pure article and is methylene-succinic acid mono 141.3g, and yield is 65.8%, product purity 97.50%.
Claims (5)
1. the preparation method of a methylene-succinic acid mono, this method comprises the steps:
Step 1. is a raw material with methylene-succinic acid and propyl carbinol under condition of normal pressure, adds catalyzer, stopper and band aqua simultaneously, carries out esterification, and esterification reaction temperature is 80～130 ℃, and the reaction times is 3～7 hours; The reaction mol ratio of said methylene-succinic acid and propyl carbinol is 1: 0.9～1.3; Said catalyzer is toluenesulphonic acids, sodium-acetate or sodium pyrosulfate, and said stopper is MEHQ, Resorcinol or phenothiazine, and said band aqua is sherwood oil, hexanaphthene or toluene; Said catalyst consumption is 0.1～0.2% of total inventory, and the consumption of said stopper is 0.05～0.2% of total inventory, and the consumption of said band aqua is 10～20% of total inventory; Said total inventory is meant the total mass of methylene-succinic acid, propyl carbinol, catalyzer, stopper and band aqua before the reaction;
Step 2. esterification adds entry after finishing in the reaction product system, after extraction treatment, collect organic phase, and this organic phase is carried out obtaining thick product after vacuum hydro-extraction is handled;
Step 3. is handled the thick product of step 2 preparation gained again through low temperature crystallization, the gained xln is required methylene-succinic acid mono after the spinning, and said low temperature crystallization treatment temperature is 7～16 ℃.
2. according to the preparation method of the said a kind of methylene-succinic acid mono of claim 1, it is characterized in that said band aqua is a hexanaphthene.
3. according to the preparation method of the said a kind of methylene-succinic acid mono of claim 1, the consumption that it is characterized in that said stopper is 0.05～0.1% of total inventory.
4. according to the preparation method of the said a kind of methylene-succinic acid mono of claim 1, it is characterized in that in the step 1 that the temperature of said esterification is 90～120 ℃, the reaction times is 4～6 hours.
5. according to the preparation method of the said a kind of methylene-succinic acid mono of claim 1, it is characterized in that said low temperature crystallization treatment temperature is 10～12 ℃.
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| CN103360251B (en) * | 2012-03-26 | 2015-03-18 | 中国科学院上海硅酸盐研究所 | Method for catalytically synthesizing mono-butyl itaconate at high selectivity |
| CN104530404B (en) * | 2015-01-19 | 2016-08-24 | 广东希贵光固化材料有限公司 | Preparation method of multifunctional acrylate oligomer |
| CN111321176B (en) * | 2020-03-11 | 2021-11-09 | 北京化工大学 | Method for preparing 4-monooctyl itaconate by enzymatic selective catalysis |
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