CN109180538A - A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield - Google Patents
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield Download PDFInfo
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- CN109180538A CN109180538A CN201811096394.XA CN201811096394A CN109180538A CN 109180538 A CN109180538 A CN 109180538A CN 201811096394 A CN201811096394 A CN 201811096394A CN 109180538 A CN109180538 A CN 109180538A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
Abstract
The present invention provides a kind of production method for improving three monomer synthesis M-phthalic acid -5- sulfonic acid yields, it is characterized by: the production method, including feed, be filled with nitrogen, first stage temperature reaction, second stage temperature reaction, remaining oleum, phase III temperature reaction, negative reaction be added.What the present invention obtained has the beneficial effect that the shortening reaction time, reduces reaction temperature；It is compared with existing production technology, maximum temperature reduces by 30 DEG C, sulfonating reaction cycle time 2 hours；Sulfur trioxide loss is reduced, cost is reduced, improves three monomer product economic benefits；Oleum dosage is reduced, and reduces 5% than prior art dosage, it is possible to reduce subsequent 5% or more neutralization step alkali charge, while shortening the neutralization step reaction time, the dosage of cooling water is reduced, energy-saving effect is significant；Improve M-phthalic acid -5- sulfonic acid yield.
Description
Technical field
The invention belongs to technical field of organic synthesis, in particular to M-phthalic acid is weight when starting material synthesizes three monomers
The synthesis for the intermediate M-phthalic acid -5- sulfonic acid wanted.
Background technique
Using M-phthalic acid as starting material synthesize three monomers (chemical name: Sodium Dimethyl Isophthalate-5-sulfonate,
English abbreviation is SIPM), due to the difference of synthesis technology and raw material, production method is essentially divided into following several: (1) sulfonic acid knot
M-phthalic acid sulfur trioxide or oleum are carried out sulfonation by crystallization, and sulfonation mother liquor is then diluted to sulfuric acid with ice water
Mass fraction is 50%-70%, and sulfonic acid is precipitated in crystallization, then removes extra spent acid, is esterified with excessive methanol, it is laggard
Row is neutralized, is refined, and SIPM is made；(2) it is esterified sulfonation method, M-phthalic acid first adds methanol to be esterified, produces M-phthalic acid
Then dimethyl ester is mixed with M-phthalic acid, with sulfur trioxide (S03) or oleum progress sulfonation, later to isophthalic diformazan
The mixture of dimethyl phthalate-monosulfonic acid and M-phthalic acid monosulfonic acid is esterified, neutralizes, is refining to obtain SIPM；(3) chlorosulfonic acid sulphur
Change, be sulfonating agent progress sulfonation using chlorosulfonic acid, it is neutralized, be separated by filtration after dry to obtain 5-sodium sulfo isophthalate, then through ester
Change, neutralize, final refining obtains SIPM；(4) oleum " is treated different things alike " method, by the oleum of M-phthalic acid various concentration
Sulfonation, sulfonated bodies without isolation, are directly esterified using the useless acid as catalyst of residue, then it is neutralized, be refining to obtain SIPM.Its
The advantages that middle oleum method has simple production process, and high income, production cost is low, stable product quality, environmental pollution is small,
It is generallyd use by industry, is the production technology mainly used in current production.
M-phthalic acid -5- sulfonic acid is prepared using various concentration oleum, then produces three monomers, the country has carried out work
Make, main results have:
Li Bingbing in Petroleum Univ.'s Master's thesis, " grind by the synthesis of 1,3- rutgers -5- sodium sulfonate and performance
Study carefully " proposed in (in May, 2012) 1,3- phthalic acid using 22% oleum synthesis M-phthalic acid -5- sulfonic acid it is small
Trial work skill, it is said that M-phthalic acid -5- sulfonic acid yield is up to 99.2%, but there are cumbersome, long preparation periods, product analysis
The defects such as purity is low.
Lee Guoqiang of Qingdao University of Science and Technology, Tang Xuli, Wen Lirong etc. publish thesis in " fine chemistry industry " (the 1st phase in 2003)
" synthesis of Sodium Dimethyl Isophthalate-5-sulfonate ", proposing using the oleum of concentration 30% is sulfonating agent and isophthalic two
Formic acid reaction, first prepares the technique of M-phthalic acid -5- sulfonic acid reproduction Sodium Dimethyl Isophthalate-5-sulfonate (SIPM).
Although sulfonation optimum process condition has been determined, intermediate control analysis, sulfur trioxide are not carried out to M-phthalic acid -5- sulfonic acid
Dosage is bigger than normal, and subsequent handling carries out neutralization temperature using alkali and needs low-temperature cooling media energy consumption higher for 23 DEG C.
Shanghai University Of Engineering Science Zhang Huifang, Shen Yong, Sun Nan etc. was " Shanghai University Of Engineering Science's journal " (2002 the 3rd
Phase) publish thesis " SIPM synthesising process research ", and it proposes and is reacted using the oleum of 60% or more concentration with phthalic acid,
First prepare the technique of M-phthalic acid -5- sulfonic acid reproduction Sodium Dimethyl Isophthalate-5-sulfonate (SIPM).Although proposing
The analysis method of sulphonation rate, but error is larger；Under determining optimum condition, sulfur trioxide is with M-phthalic acid molar ratio
1.3, and reaction temperature is higher.
Chinese patent (patent No.: 201210072769.5, patent name: isophthalic diformazan is prepared with high concentration fuming sulfuric acid
The method of dimethyl phthalate -5- sodium sulfonate) in propose M-phthalic acid and 60-70% oleum in 1:(0.92-1.08)
Weight ratio, prepare within sulfonating reaction 10 hours sulfonated bodies M-phthalic acid -5- sulfonic acid method at 150 DEG C.The deficiency of this method
Place is: the sulfonating reaction time is long, does not carry out intermediate control analysis to M-phthalic acid -5- sulfonic acid.
Chinese patent (patent No.: 201210078339.4, a kind of patent name: dimethyl isophthalate -5- sulfonic acid
The synthetic method of sodium) in propose M-phthalic acid and 64-68% oleum in the presence of catalyst sulfuric acid cadmium, mercuric sulfate,
It is simultaneously the technique of side reaction inhibitor progress sulfonation using anhydrous sodium sulfate and silica.The shortcoming of this method is:
The use of toxic heavy metal compound is catalyst, makes troubles to subsequent processing and environmental pollution etc.；Make under different temperatures
With different catalyst, cumbersome, operational danger is big；The sulfonating reaction time is long, temperature drift, not to isophthalic diformazan
Acid -5- sulfonic acid carries out intermediate control analysis.
M-phthalic acid -5- sulfonic acid is prepared in conclusion reacting in the prior art using M-phthalic acid with oleum
Then three monomers are produced, wherein preparing intermediate M-phthalic acid -5- sulfonic acid technique is primarily present following technical problem:
(1) reaction temperature is higher, and the reaction temperature that some technique uses is up to 220 DEG C.
(2) reaction time is long, and some technological reaction time is more than 10 hours.
(3) yield of M-phthalic acid -5- sulfonic acid is low, and the yield of lab scale is more than 99% in existing research achievement, but industrializes
Yield is relatively low in production, although only 83% or so being then not difficult to extrapolate from the yield of three monomer of final products without data report
The yield of M-phthalic acid -5- sulfonic acid is no more than 97%.
(4) dosage of sulfur trioxide is bigger than normal in the prior art.
(5) the use of heavy metal compound is catalyst, makes troubles to subsequent catalyst processing, it is possible to cause environment dirty
It contaminates and handles cumbersome.
(6) using a variety of auxiliary agents as catalyst, side reaction inhibitor, operating process is complicated and has certain risk.
(7) do not quantitatively determine the analysis method of M-phthalic acid -5- sulfonic acid yield, or using simple chemical titration,
The yield of potentiometry, gravimetric detemination M-phthalic acid -5- sulfonic acid, due to M-phthalic acid -5- sulfonic acid, impurity is more, containing more
Kind different structure contains multiple sulfonic benzene ring compounds, can be made using simple chemical titration, potentiometry, gravimetric method etc.
It is higher at analysis result.
Summary of the invention
Synthesize with oleum M-phthalic acid -5- sulfonic acid for domestic existing M-phthalic acid there are yields it is low, react
Temperature drift, the reaction time is long, raw material proportioning is unreasonable, leads to that three monomer of final products is at high cost, impurity content is high,
The present invention furthers investigate material proportion, reaction temperature and time etc., optimizes to prior art, forms new work
Skill.The invention main purpose is:
1, shorten the reaction time, reduce reaction temperature；
2, sulfur trioxide loss is reduced, cost is reduced, improves three monomer product economic benefits；
3, M-phthalic acid -5- sulfonic acid yield is improved；
4, it establishes M-phthalic acid and synthesizes isophthalic diformazan in the acidification feed liquid that M-phthalic acid -5- sulfonic acid obtains with oleum
Acid -5- sulfonic acid fast and accurately analysis method；
5, catalyst is made without the use of heavy metal compound or a variety of auxiliary agents.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield, comprising the following steps:
(1) it feeds
The oleum of total amount 80% is put into sulphonation kettle, opens stirring；Whole M-phthalic acids is added in 50-70 minutes
Enter sulphonation kettle；
M-phthalic acid: 65% oleum (weight ratio)=1.168-1.186:1.
(2) it is filled with nitrogen
M-phthalic acid finishes, and nitrogen is filled with into sulphonation kettle, and when nitrogen pressure reaches 0.01-0.015MPa, (gauge pressure is pressed
The data that power table is shown, similarly hereinafter), it closes nitrogen and valve is added, start to heat up.
(3) first stage temperature reaction
Sulphonation kettle kettle temperature is risen to 120-125 DEG C from room temperature in 40-70 minutes, is reacted 50-80 minutes.
(4) second stage temperature reaction
At 120-125 DEG C after reaction 50-80 minutes, sulphonation kettle kettle temperature is risen into 140-145 from 120-125 DEG C in 40-60 minutes
DEG C, nitrogen purge valve is opened after reacting 50-80 minutes at such a temperature.
(5) remaining oleum is added
It is down to after pressure gauge is shown as 0 after pressure in sulphonation kettle kettle, the oleum of remaining total amount 20% is added.
(6) phase III temperature reaction
Remaining oleum finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa,
It closes nitrogen and valve is added, continue to heat up to sulphonation kettle.Adjusting reaction temperature is 155-160 DEG C, and the reaction was continued, and 50-80 divides
Clock.
(7) negative reaction
When observe sulphonation kettle temperature be higher than 160 DEG C and it is in rising trend when, open nitrogen purge valve, to pressure in sulphonation kettle kettle
It is down to after data that pressure gauge is shown are 0, opens vacuum pump and sulphonation kettle is vacuumized, vacuum degree is 0.05- in sulphonation kettle kettle
0.08MPa, control reaction temperature are no more than 165 DEG C.Under the conditions of vacuum degree is 0.05-0.08MPa, 160 DEG C -165 DEG C of temperature
The reaction was continued 50-80 minutes.
Sampling, using the purity of M-phthalic acid -5- sulfonic acid in material in liquid chromatography analysis sulphonation kettle.In sulphonation kettle
Material is put into esterifying kettle and methanol carries out esterification, then by neutralization, purification, dry obtained three monomers.
(later abbreviation sulfonation material) M-phthalic acid -5- sulfonic acid content measures in the material of end of reaction in above-mentioned sulphonation kettle
Technological parameter is as follows:
1, instrument:
(1) FL2200 liquid chromatograph matches UV detector, N2000 chromatographic work station
(2) 5 μm of 4.6 × 250mm of chromatographic column Kromstar C18
(3) thermocolumn case: day Puli RPL-C2000
(4) ultrasonic degasser.
2, testing conditions:
(1) mobile phase: a. water.B. methanol (chromatographically pure).Proportion of mobile phase Va:VbIt is dripped in=1:1,1000ml mixed flow phase
Add 10 drop phosphoric acid；
(2) Detection wavelength: 230nm(is determined with diode array detector)；
(3) flow velocity: 0.8mL/min；
(4) sampling volume: 20 μ L；
(5) column temperature: 30 DEG C.
3, sample treatment:
0.05g sulfonation material is accurately weighed, is dissolved with mobile phase a, constant volume deaerates after the filtering of water system film in 100mL volumetric flask
It is spare.
4, detecting step:
It requires to carry out mobile phase pre-treatment according to liquid chromatograph operation, booting preheating is extracted to test sample after the system stabilizes
20 μ L sample detection of product, to appearance after, with area normalization method calculate percentage composition.
Beneficial effects of the present invention:
1, shorten the reaction time, reduce reaction temperature；
It is compared with existing production technology, maximum temperature reduces by 30 DEG C, sulfonating reaction cycle time 2 hours.
Reaction temperature of the invention is divided into 4 stages: 120-125 DEG C, 140-145 DEG C, 155-160 DEG C, 160 DEG C -165
DEG C, maximum temperature≤165 DEG C；
Reaction time of the invention about 8 hours, the existing industrialization process reaction time was more than 10 hours.
2, sulfur trioxide loss is reduced, cost is reduced, improves three monomer product economic benefits；
Oleum dosage is reduced, and reduces 5% than prior art dosage, it is possible to reduce subsequent 5% or more neutralization step alkali charge, together
When shorten the neutralization step reaction time, reduce the use of cooling water (cooling water temperature that neutralization step uses at present be 10 DEG C or so)
Amount, energy-saving effect are significant.
3, M-phthalic acid -5- sulfonic acid yield is improved.
It is applied on commercial plant, the yield of M-phthalic acid -5- sulfonic acid is 98.96-99.15%, and three monomers of preparation produce
Quality reaches top grade product standard (company standard), and yield is more than 86.2%.
4, the optimised process of the content of M-phthalic acid -5- sulfonic acid in material in liquid chromatography analysis sulphonation kettle has been determined
Parameter, this method have the distinguishing features such as quick, accurate, easy, reproducible.
5, operational safety improves.
Detailed description of the invention
Fig. 1 is the spectrogram of the liquid chromatogram of M-phthalic acid -5- sulfonic acid prepared by the embodiment of the present invention 6.
Specific embodiment
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield of embodiment 1
The following steps are included:
(1) it feeds
Material proportion: 1900 kilograms of M-phthalic acid；65% 1620 kilograms of oleum；Reaction in 3000L glass-lined kettle into
Row；
Head tank is squeezed into 1620 kilograms of oleum metering, 1300 kilograms of oleum is put into sulphonation kettle, unlatching is stirred
It mixes；Sulphonation kettle is added in 60 minutes in 1900 kilograms of M-phthalic acids.
(2) it is filled with nitrogen
M-phthalic acid finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, closes nitrogen and valve is added,
Start to heat up.
(3) first stage temperature reaction
Sulphonation kettle kettle temperature is risen to 120 DEG C from room temperature in 40 minutes, maintains reaction 60 minutes.
(4) second stage temperature reaction
It is reacted at 120 DEG C after sixty minutes, sulphonation kettle kettle temperature is risen to 140 DEG C from 120 DEG C in 50 minutes, reaction is opened after sixty minutes
Nitrogen purge valve.
(5) remaining oleum is added
It is down to after pressure gauge is shown as 0 after pressure in sulphonation kettle kettle, remaining oleum is added from head tank.
(6) phase III temperature reaction
Remaining oleum finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, closes nitrogen and adds
Enter valve, continue to heat up to sulphonation kettle, adjustment reaction temperature is 155 DEG C, and the reaction was continued 50 minutes.
(7) negative reaction
When observe sulphonation kettle temperature be higher than 160 DEG C and it is in rising trend when, open nitrogen purge valve, to pressure in sulphonation kettle kettle
It is down to after data that pressure gauge is shown are 0, opens vacuum pump and sulphonation kettle is vacuumized, vacuum degree is in sulphonation kettle kettle
0.055MPa, control reaction temperature are no more than 165 DEG C.The reaction was continued 60 under the conditions of vacuum degree is 0.055MPa, 165 DEG C of temperature
Minute.
Sampling, using the purity of the M-phthalic acid -5- sulfonic acid in material in liquid chromatography analysis sulphonation kettle.Analysis knot
Fruit: the purity of M-phthalic acid -5- sulfonic acid is 98.77%, yield 99.05%.
Material is put into esterifying kettle and methanol progress esterification in sulphonation kettle, then by neutralization, purification, dry obtained three
Monomer.SIPM product quality indicator such as the following table 1 of preparation.
The SIPM product quality indicator of 1 embodiment of the present invention 1 of table preparation
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield of embodiment 2
The following steps are included:
(1) it feeds
Material proportion: 1925 kilograms of M-phthalic acid；65% 1645 kilograms of oleum；Reaction in 3000L glass-lined kettle into
Row.
Head tank is squeezed into 1645 kilograms of oleum metering, 1320 kilograms of oleum is put into sulphonation kettle, is opened
Open stirring；Sulphonation kettle is added in 50 minutes in 1925 kilograms of M-phthalic acids.
(2) it is filled with nitrogen
M-phthalic acid finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, closes nitrogen and valve is added,
Start to heat up.
(3) first stage temperature reaction
Sulphonation kettle kettle temperature is risen to 122 DEG C from room temperature in 50 minutes, maintains reaction 70 minutes by the first stage.
(4) second stage temperature reaction
Sulphonation kettle kettle temperature is risen to 142 DEG C from 122 DEG C in 60 minutes, reaction 60 after 122 DEG C are reacted 70 minutes by second stage
Nitrogen purge valve is opened after minute.
(5) remaining oleum is added
It is down to after data that pressure gauge is shown are 0 after pressure in sulphonation kettle kettle, remaining oleum is added from head tank.
(6) phase III temperature reaction
Remaining oleum finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, closes nitrogen and adds
Enter valve, continues to heat up to sulphonation kettle.Adjusting reaction temperature is 155 DEG C, and the reaction was continued 60 minutes.
(7) negative reaction
When observe sulphonation kettle temperature be higher than 160 DEG C and it is in rising trend when, open nitrogen purge valve, to pressure in sulphonation kettle kettle
It is down to after data that pressure gauge is shown are 0, opens vacuum pump and sulphonation kettle is vacuumized, vacuum degree is in sulphonation kettle kettle
0.066MPa, control reaction temperature are no more than 165 DEG C.The reaction was continued 70 under the conditions of vacuum degree is 0.066MPa, 162 DEG C of temperature
Minute.
Sampling, using the purity of the M-phthalic acid -5- sulfonic acid in liquid chromatography analysis sulfonation material.Analyze result:
The purity of phthalic acid -5- sulfonic acid is 98.56%, yield 99.15%；
Material is put into esterifying kettle and methanol progress esterification in sulphonation kettle, then passes through neutralization, purification, dry obtained three list
Body.SIPM product quality indicator such as the following table 2 of preparation.
The SIPM product quality indicator of 2 embodiment of the present invention 2 of table preparation
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield of embodiment 3
The following steps are included:
(1) it feeds
Material proportion: 1950 kilograms of M-phthalic acid；65% 1660 kilograms of oleum；Reaction in 3000L glass-lined kettle into
Row.
Head tank is squeezed into 1660 kilograms of oleum metering, 1330 kilograms of oleum is put into sulphonation kettle, is opened
Open stirring；Sulphonation kettle is added in 60 minutes in 1950 kilograms of M-phthalic acids.
(2) it is filled with nitrogen
M-phthalic acid finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.012MPa, closes nitrogen and is added
Valve starts to heat up.
(3) first stage temperature reaction
Sulphonation kettle kettle temperature is risen to 124 DEG C from room temperature in 60 minutes, maintains reaction 80 minutes by the first stage.
(4) second stage temperature reaction
Sulphonation kettle kettle temperature is risen to 145 DEG C from 124 DEG C in 45 minutes, reaction 55 after 124 DEG C are reacted 80 minutes by second stage
Nitrogen purge valve is opened after minute.
(5) remaining oleum is added
It is down to after data that pressure gauge is shown are 0 after pressure in sulphonation kettle kettle, remaining oleum is added from head tank.
(6) phase III temperature reaction
Remaining oleum finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, closes nitrogen and adds
Enter valve, continues to heat up to sulphonation kettle.Adjusting reaction temperature is 156 DEG C, and the reaction was continued 70 minutes.
(7) negative reaction
When observe sulphonation kettle temperature be higher than 160 DEG C and it is in rising trend when, open nitrogen purge valve, to pressure in sulphonation kettle kettle
It is down to after data that pressure gauge is shown are 0, opens vacuum pump and sulphonation kettle is vacuumized, vacuum degree is 0.07MPa in sulphonation kettle kettle,
It controls reaction temperature and is no more than 165 DEG C.The reaction was continued 65 minutes under the conditions of vacuum degree is 0.07MPa, 164 DEG C of temperature.
Sampling, using the purity of the M-phthalic acid -5- sulfonic acid in liquid chromatography analysis sulfonation material.Analyze result:
The purity of phthalic acid -5- sulfonic acid is 98.74%, yield 98.96%；
Material is put into esterifying kettle and methanol progress esterification in sulphonation kettle, then passes through neutralization, purification, dry obtained three list
Body.SIPM product quality indicator such as the following table 3 of preparation.
The SIPM product quality indicator of 3 embodiment of the present invention 3 of table preparation
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield of embodiment 4
The following steps are included:
(1) it feeds
Material proportion: 1975 kilograms of M-phthalic acid；65% 1675 kilograms of oleum；Reaction in 3000L glass-lined kettle into
Row.
Head tank is squeezed into 1675 kilograms of oleum metering, 1340 kilograms of oleum is put into sulphonation kettle, is opened
Open stirring；Sulphonation kettle is added in 70 minutes in 1975 kilograms of M-phthalic acids.
(2) it is filled with nitrogen
M-phthalic acid finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.014MPa, closes nitrogen and is added
Valve starts to heat up.
(3) first stage temperature reaction
Sulphonation kettle kettle temperature is risen to 125 DEG C from room temperature in 70 minutes, maintains reaction 65 minutes.
(4) second stage temperature reaction
After 125 DEG C are reacted 65 minutes, sulphonation kettle kettle temperature is risen to 145 DEG C from 125 DEG C in 55 minutes, reaction is opened after sixty minutes
Nitrogen purge valve.
(5) remaining oleum is added
It is down to after data that pressure gauge is shown are 0 after pressure in sulphonation kettle kettle, remaining oleum is added from head tank.
(6) phase III temperature reaction
Phase III, remaining oleum finish, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, close
It closes nitrogen and valve is added, continue to heat up to sulphonation kettle.Adjusting reaction temperature is 160 DEG C, and the reaction was continued 65 minutes.
(7) negative reaction
When observe sulphonation kettle temperature be higher than 160 DEG C and it is in rising trend when, open nitrogen purge valve, to pressure in sulphonation kettle kettle
It is down to after data that pressure gauge is shown are 0, opens vacuum pump and sulphonation kettle is vacuumized, vacuum degree is in sulphonation kettle kettle
0.065MPa, control reaction temperature are no more than 165 DEG C.The reaction was continued 70 under the conditions of vacuum degree is 0.065MPa, 162 DEG C of temperature
Minute.
Sampling, using the purity of the M-phthalic acid -5- sulfonic acid in liquid chromatography analysis sulfonation material.Analyze result:
The purity of phthalic acid -5- sulfonic acid is 98.82%, yield 99.11%；
Material is put into esterifying kettle and methanol progress esterification in sulphonation kettle, then passes through neutralization, purification, dry obtained three list
Body.SIPM product quality indicator such as the following table 4 of preparation.
The SIPM product quality indicator of 4 embodiment of the present invention 4 of table preparation
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield of embodiment 5
The following steps are included:
(1) it feeds
Material proportion: 2000 kilograms of M-phthalic acid；65% 1695 kilograms of oleum；Reaction in 3000L glass-lined kettle into
Row.
Head tank is squeezed into 1675 kilograms of oleum metering, 1360 kilograms of oleum is put into sulphonation kettle, is opened
Open stirring；Sulphonation kettle is added in 80 minutes in 2000 kilograms of M-phthalic acids.
(2) it is filled with nitrogen
M-phthalic acid finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, closes nitrogen and valve is added,
Start to heat up.
(3) first stage temperature reaction
Sulphonation kettle kettle temperature is risen to 120 DEG C from room temperature in 70 minutes, maintains reaction 70 minutes.
(4) second stage temperature reaction
Sulphonation kettle kettle temperature is risen to 145 DEG C from 120 DEG C in 60 minutes, reaction 75 after 120 DEG C are reacted 70 minutes by second stage
Nitrogen purge valve is opened after minute.
(5) remaining oleum is added
It is down to after data that pressure gauge is shown are 0 after pressure in sulphonation kettle kettle, remaining oleum is added from head tank.
(6) phase III temperature reaction
Phase III, remaining oleum finish, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, close
It closes nitrogen and valve is added, continue to heat up to sulphonation kettle.Adjusting reaction temperature is 155 DEG C, and the reaction was continued 80 minutes.
(7) negative reaction
When observe sulphonation kettle temperature be higher than 160 DEG C and it is in rising trend when, open nitrogen purge valve, to pressure in sulphonation kettle kettle
It is down to after data that pressure gauge is shown are 0, opens vacuum pump and sulphonation kettle is vacuumized, vacuum degree is in sulphonation kettle kettle
0.072MPa, control reaction temperature are no more than 165 DEG C.The reaction was continued 80 under the conditions of vacuum degree is 0.072MPa, 162 DEG C of temperature
Minute.
Sampling, using the purity of the M-phthalic acid -5- sulfonic acid in liquid chromatography analysis sulfonation material.Analyze result:
The purity of phthalic acid -5- sulfonic acid is 98.69%, yield 99.08%；
Material is put into esterifying kettle and methanol progress esterification in sulphonation kettle, then passes through neutralization, purification, dry obtained three list
Body.SIPM product quality indicator such as the following table 5 of preparation.
The SIPM product quality indicator of 5 embodiment of the present invention 5 of table preparation
A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield of embodiment 6
The following steps are included:
(1) it feeds
Material proportion: 2025 kilograms of M-phthalic acid；65% 1730 kilograms of oleum；Reaction in 3000L glass-lined kettle into
Row.
Head tank is squeezed into 1730 kilograms of oleum metering, 1385 kilograms of oleum is put into sulphonation kettle, is opened
Open stirring；Sulphonation kettle is added in 60 minutes in 2025 kilograms of M-phthalic acids.
(2) it is filled with nitrogen
M-phthalic acid finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.014MPa, closes nitrogen and is added
Valve starts to heat up.
(3) first stage temperature reaction
Sulphonation kettle kettle temperature is risen to 124 DEG C from room temperature in 60 minutes, maintains reaction 75 minutes.
(4) second stage temperature reaction
Sulphonation kettle kettle temperature is risen to 145 DEG C from 124 DEG C in 48 minutes, reaction 55 after 124 DEG C are reacted 75 minutes by second stage
Nitrogen purge valve is opened after minute.
(5) remaining oleum is added
It is down to after data that pressure gauge is shown are 0 after pressure in sulphonation kettle kettle, remaining oleum is added from head tank.
(6) phase III temperature reaction
Remaining oleum finishes, and nitrogen is filled with into sulphonation kettle, when nitrogen pressure reaches 0.01MPa, closes nitrogen and adds
Enter valve, continues to heat up to sulphonation kettle.Adjusting reaction temperature is 158 DEG C, and the reaction was continued 70 minutes.
(7) negative reaction
When observe sulphonation kettle temperature be higher than 160 DEG C and it is in rising trend when, open nitrogen purge valve, to pressure in sulphonation kettle kettle
It is down to after data that pressure gauge is shown are 0, opens vacuum pump and sulphonation kettle is vacuumized, vacuum degree is 0.07MPa in sulphonation kettle kettle,
It controls reaction temperature and is no more than 165 DEG C.The reaction was continued 65 minutes under the conditions of vacuum degree is 0.07MPa, 164 DEG C of temperature.
Sampling, using the purity of the M-phthalic acid -5- sulfonic acid in liquid chromatography analysis sulfonation material.Analyze result:
The purity of phthalic acid -5- sulfonic acid is 98.84%, yield 99.12%；
Material is put into esterifying kettle and methanol progress esterification in sulphonation kettle, then passes through neutralization, purification, dry obtained three list
Body.SIPM product quality indicator such as the following table 6 of preparation.
The SIPM product quality indicator of 6 embodiment of the present invention 6 of table preparation
Material (the later abbreviation sulfonation material) M-phthalic acid -5- sulfonic acid content measurement technique ginseng of end of reaction in above-mentioned sulphonation kettle
Number is as follows:
1, instrument:
(1) FL2200 liquid chromatograph matches UV detector, N2000 chromatographic work station
(2) 5 μm of 4.6 × 250mm of chromatographic column Kromstar C18
(3) thermocolumn case: day Puli RPL-C2000
(4) ultrasonic degasser.
2, testing conditions:
(1) mobile phase: a. water.B. methanol (chromatographically pure).Proportion of mobile phase Va:VbIt is dripped in=1:1,1000ml mixed flow phase
Add 10 drop phosphoric acid；
(2) Detection wavelength: 230nm(is determined with diode array detector)；
(3) flow velocity: 0.8mL/min；
(4) sampling volume: 20 μ L；
(5) column temperature: 30 DEG C.
3, sample treatment:
0.05g sulfonation material is accurately weighed, is dissolved with mobile phase a, constant volume deaerates after the filtering of water system film in 100mL volumetric flask
It is spare.
4, detecting step:
It requires to carry out mobile phase pre-treatment according to liquid chromatograph operation, booting preheating is extracted to test sample after the system stabilizes
20 μ L sample detection of product, to appearance after, with area normalization method calculate percentage composition.
The results are shown in attached figure 1 and table 7 for analysis, in attached drawing 1 and table 7:
1 is two sulfonated bodies of M-phthalic acid；2 be three sulfonated bodies of M-phthalic acid；3 be M-phthalic acid -5- sulfonic acid；4 be isophthalic
Dioctyl phthalate；5 be polymer (structure is unknown)；6 be oxide (structure is unknown).
The liquid chromatogram appearance result of each component in 7 sulfonation material of table
Sulphonation kettle is added in two portions in oleum in the present invention, and M-phthalic acid is added at one time, and total amount 80% is added early period in reaction
Oleum, the molar ratio of M-phthalic acid and sulfur trioxide is higher than 1, and the sulfur trioxide overwhelming majority is located in -5- on phenyl ring
On position (two carboxyl numbers of M-phthalic acid are 1.3 positions), multidigit sulfonated bodies quantity is seldom；It is remaining to react later period addition
Oleum, the unreacted M-phthalic acid continuation in part is reacted with sulfur trioxide, in this way, greatly reducing multidigit sulfonated bodies
Amount, decreases the generation of sulfone compound.
It reacts and uses low temperature, positive pressure operation early period, reduce loss of the sulfur trioxide from sulphonation kettle, sulfur trioxide is almost complete
Portion participates in reaction；After second of oleum is added, the reaction later period uses negative-pressure operation, enhances sulphur under one side vacuum condition
The stirring for changing material in kettle, promotes heat and mass transfer, on the other hand reduces reaction temperature, reduce side reaction.
Control by stages temperature, sulfonic group positioning reduces more sulphurs substantially on phenyl ring number -5- in sulfonating reaction
The generation of compound；Since M-phthalic acid is exothermic reaction with reacting for oleum, reaction temperature is higher, side reaction and by-product
Object is more, using control by stages temperature, can make full use of the heat of reaction releasing to sulfonating reaction gradient increased temperature, reduces
The dosage of heat medium and heating time, energy-saving effect are significant；Reacting balance avoids hot-spot and polymerization, coking, oxygen occurs
The side reactions such as change.
Unless specifically indicated, the percentage that the present invention uses, is mass percent, and the ratio of use is mass ratio
Example, the pressure after heretofore described inflated with nitrogen are gauge pressure, i.e., the data that shows of pressure gauge, normal pressure are shown as 0 for pressure gauge.
Claims (8)
1. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield, it is characterised in that: the production
Method, including feed, be filled with nitrogen, first stage temperature reaction, second stage temperature reaction, remaining oleum, the be added
The reaction of three step-up temperatures, negative reaction.
2. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield according to claim 1,
It is characterized by: the charging, is added the oleum for accounting for total amount 80%, adds M-phthalic acid；M-phthalic acid and smoke
The weight ratio of sulfuric acid total amount is 1.168-1.186:1；The concentration of the oleum is 65%.
3. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield according to claim 1,
It is characterized by: described be filled with nitrogen, it is filled with nitrogen to pressure and reaches 0.01-0.015MPa.
4. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield according to claim 1,
It is characterized by: the first stage temperature reaction, rises to 120-125 DEG C from room temperature for kettle temperature in 40-70 minutes, reacts 50-
80 minutes.
5. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield according to claim 1,
It is characterized by: the second stage temperature reaction, rose to 140-145 DEG C from 120-125 DEG C for kettle temperature in 40-60 minutes,
Nitrogen purge valve is opened after reacting 50-80 minutes at this temperature.
6. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield according to claim 1,
It is characterized by: the remaining oleum of the addition, it is down to after pressure gauge is shown as 0 after pressure, remaining total amount 20% is added
Oleum.
7. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield according to claim 1,
It is characterized by: the phase III temperature reaction, when to be filled with nitrogen to pressure be 0.01MPa, adjustment reaction temperature is 155-
160 DEG C, the reaction was continued 50-80 minutes.
8. a kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield according to claim 1,
It is characterized by: the negative reaction, the reaction was continued under the conditions of vacuum degree is 0.05-0.08MPa, 160 DEG C -165 DEG C of temperature
50-80 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110907551A (en) * | 2019-11-30 | 2020-03-24 | 山东第一医科大学(山东省医学科学院) | Method for detecting purity of dimethyl isophthalate-5-sulfonic acid in esterification liquid for producing three monomers |
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