Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of productive rate height, product purity height, 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 by following scheme:
A kind of preparation method of methylene-succinic acid mono, this method is under condition of normal pressure, with methylene-succinic acid and propyl carbinol is raw material, simultaneously in addition suitable reaction promoter, esterification takes place at a certain temperature, finish 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 was carried out vacuum hydro-extraction and handled, the thick product of gained was handled through low temperature crystallization again, the gained xln is finished product after the centrifugation, 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 a significant impact, therefore, after the inventor has carried out a large amount of tests and has groped these factors, obtain following data, adopt following optimization data, 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, described 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 described 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, by 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 band aqua and the unreacted propyl carbinol that to remove in the reaction product system by vacuum hydro-extraction.
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, 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 to be handled, 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 again with solid-liquid separation, 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 is by handling, and can prepare dibutyl itaconate content and reach dibutyl itaconate product more than 98%, sells as byproduct.
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, the methylene-succinic acid mono that does not crystallize out can 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 reaction finishes the collocation of the various processing schemes in back, finally obtain a kind of preparation method of methylene-succinic acid mono, the methylene-succinic acid mono that adopts the preparation of this method is the yield height not only, can be up to 60~75%, and purity is also very high, can reach more than 97%, in addition, this preparation 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, with methylene-succinic acid and propyl carbinol is raw material, simultaneously in addition suitable reaction promoter, esterification takes place at a certain temperature, finish 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 was carried out vacuum hydro-extraction and handled, the thick product of gained was handled through low temperature crystallization again, the gained xln is finished product after the centrifugation, 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 a significant impact, therefore, after the inventor has carried out a large amount of tests and has groped these factors, obtain following data, adopt following optimization data, 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.
Described catalyzer adopts tosic acid, sodium-acetate or sodium pyrosulfate, catalyst consumption is 0.1~0.2% of total inventory, and described 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, by 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 band aqua and the unreacted propyl carbinol that to remove in the reaction product system by vacuum hydro-extraction.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, 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 again with solid-liquid separation, 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, thermometer, water trap and condenser 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, cool to 60 ℃, add the stirring of 300g pure water and be 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. is in the four-hole boiling flask that whipping appts, thermometer, water trap and condenser are housed, the methylene-succinic acid that adds 150g (1.15mol), 0.5g catalyzer (sodium-acetate), 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 product 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. is in the four-hole boiling flask that whipping appts, thermometer, water trap and condenser are housed, the methylene-succinic acid that adds 150g (1.15mol), 0.5g catalyst sulfuric acid hydrogen sodium, 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 product 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. is in the four-hole boiling flask that whipping appts, thermometer, water trap and condenser are housed, the methylene-succinic acid that adds 150g (1.15mol), 0.5g catalyzer tosic acid, 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 product 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. is in the four-hole boiling flask that whipping appts, thermometer, water trap and condenser are housed, the methylene-succinic acid that adds 150g (1.15mol), 0.5g catalyzer tosic acid, 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 product 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. is in the four-hole boiling flask that whipping appts, thermometer, water trap and condenser are housed, the methylene-succinic acid that adds 150g (1.15mol), 0.5g catalyzer tosic acid, 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 product 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. is in the four-hole boiling flask that whipping appts, thermometer, water trap and condenser are housed, the methylene-succinic acid that adds 150g (1.15mol), 0.5g catalyzer tosic acid, 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 product and is methylene-succinic acid mono 141.3g, and yield is 65.8%, product purity 97.50%.