CN102633693A - Method for synthesizing dimethyl isophthalate-5-sodium sulfonate - Google Patents
Method for synthesizing dimethyl isophthalate-5-sodium sulfonate Download PDFInfo
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Abstract
The invention discloses a method for synthesizing dimethyl isophthalate-5-sodium sulfonate. Dimethyl isophthalate-5-sodium sulfonate is prepared by steps of sulfonation reaction, esterification, neutralization reaction and aftertreatment with isophthalic acid and fuming sulfuric acid serving as raw materials, wherein the sulfonation reaction is completed in three reaction temperature zones, different catalysts are used in different reaction temperature zones, cadmium sulfate is used as the catalyst at the temperature ranging from 150 DEG C to 159 DEG C, SiO2 is used as the catalyst at the temperature ranging from 160 DEG C to 169 DEG C, and mercuric sulfate is used as the catalyst temperature ranging from 170 DEG C to 181 DEG C. By the method, sulfonation reaction effect is improved, conversion rate of isophthalic acid is increased, sulfonation reaction temperature is lowered while sulfonation reaction time is shortened, reaction by-products including disulfonate, polymer and sulfone compounds are greatly reduced, product purity is improved while product yield is increased, and further, usage of fuming sulfuric acid and usage of sodium carbonate in a subsequent neutralization procedure are reduced, so that production cost is reduced.
Description
Technical field
The present invention relates to technical field of organic synthesis, relate in particular to the compound method of a kind of dimethyl isophthalate-5-sodium sulfonate.
Background technology
Dimethyl isophthalate-5-sodium sulfonate (popular name three monomers; SIPM write a Chinese character in simplified form in English); As a kind of serious difference properties-correcting agent of producing modified poly ester product (CDP/ECDP etc.); Add co-blended spinning in the section (PET), solved that the conventional polyester water absorbability that the terylene molecular structure determined is poor, the dyeing difficulty, be easy to generate electrostatic problem, and fibre strength often makes many defectives such as the easy balling-up of fabric, its style and clothes comfortableness and natural fiber existence very big gap when too high.
In PET Resin/Poyester Chips Bottle Grade, introduce SIPM and can produce cation-modified polyester filament; Though its outward appearance does not have too big difference with the ordinary polyester long filament; But owing to adopted cation-modified; Not only improve the suction look performance of fiber greatly, and reduced percent crystallinity, thereby further adapted to the emulation silkization of trevira.Can make through the emulation silkization that fabric sofetening is ventilative, comfortable, antistatic, normal-temperature normal-pressure dyeable.Through cation-modified multi-functional simulate wool, can make fabric have characteristics such as soft, antistatic, normal temperature and pressure and Mao Gongran.When cation dyeable polyester products such as (CDP) is dyeed, can adopt low price, chromatogram cationic dyeing wide, bright in colour, still available disperse dyeing simultaneously, its dyeability has clear improvement than conventional polyester.The fabric that is made into cation-modified fiber when dyeing with cationic dyestuff, has bright, advantage such as engrain property good, fastness to light and colour fastness are good.When combination dyeing, the dyestuff consistency is good.Modified polyester fiber not only dyes more bright-coloured dense, and tint permanence is good, and has the anti effect.Good stability in the high temperature dye bath, little to the staining property of other fibers of comprising the conventional polyester fiber, fast to the rate of diffusion of fibrous inside, and the non-environmental-pollution phenomenon, pH value changes greatly in the dye bath, the dye stability height.
In recent years, be that the application of cation dyeable polyester in following field that raw material makes had breakthrough with SIPM:
1, produce sea-island fibre: with the POY sea island filament that normal polyester section blending makes, texturing process is smooth, and process stabilizing effectively improves the spinning property of sea-island fibre and workability.Sea-island fibre is mainly used in: (1) fashion material, because its ventilation property, flexibility is also more superior than natural fabric, makes chemical fiber plus material rank among the top-grade fashion field; (2) imitation leather; Ultra-fine fibre is that the PU leather of base cloth arises at the historic moment; It not only possesses the microtexture similar with natural leather; Have good water vapour permeability, dimensional stability, each item fastness is superior to natural leather, and the defective that irregularity is high, effective rate of utilization is little of having avoided natural article to cause owing to the difference at kind, size and the position of animal; (3) high-performance cloth for wiping or dusting; (4) high-performance filtering material; (5) high-performance paper; (6) bio-medical material is the focus of present textile industry research.
2, synthesizing water-solubility polyester: water-soluble polyester is a kind of new type water-solubility polymkeric substance, and it is in molecular chain, to introduce the unitary a kind of ion type copolyester of ionic structure.The existence of ionic groups gives polyester the water miscible while, has also given its good hygroscopic property and ionic conductance characteristic.Have a wide range of applications in fields such as chemical fibre, weaving, coating, tackiness agent, electronics, tensio-active agent, printing ink.Can prepare multiporous fiber through dissolving from handling, the water absorbability of fiber is improved, volume specific resistance reduces, and has improved the antistatic property of trevira.At coating and adhesive area, can be prepared into amino Baking Paint and dual-component aqueous polyurethane etc.Because the wetting ability of sulphonate is very strong, the waterborne polyester dispersion-s of preparation can improve at particle diameter, aspect stable, therefore, receives researchist's extensive concern.
People are devoted to seek new, more efficiently colloidal dispersion system stablizer in recent years, and the polyester that wherein has amphiphilic structure enjoys attention.Adopting DMT. Dimethyl p-benzenedicarboxylate and terepthaloyl moietie is main monomer; With SIPM as hydrophilic monomer; Adopt transesterify-condensation polymerization route synthesizing water-solubility polyester; In the chemical fibre field as the ultra-fine fibre conjugate spinning with molten from constituent materials have report, yet as the water-soluble polyester of stable colloid dispersion agent (or solubilizing agent), aspect theory and practice, report less.The synthetic water-soluble polyester in the hot water below 100 ℃, just has good water-solubility and stable colloid disperses characteristic of solubilizing.This aspect research and application will be opened up the application market of SIPM greatly.
3, be used to improve the polyester blend additive of dyeing polypropylene fibers property: polypropylene fibre is one of main synthon kind; Abundant raw material, price are low, light specific gravity, thermostability are high, hydrophobicity and heat retention are good, and corrosion-resistant, anti-mildew becomes, have good processing characteristics and physical and mechanical properties.But the crystalling propylene degree is high, does not have the polar group that can act on mutually with dye molecule, thereby causes its dyeing difficulty.Desire to make polypropylene fibre to have dyeability, need Vestolen PP 7052 is carried out modification, one of its method is that blending can be dyed additive.Adopt the modified poly ester of normal atmosphere cation-dyeable; Improve dyeing polypropylene fibers property through blend method; Not only reduce dyeing installation investment and energy consumption; And avoid of the damage of high-temperature pressure dyeing technology to its mixed fibre, have the dyeing of being easy to, simple to operate, low production cost in addition, chromatogram is wide, bright in colour evenly, dyefastness is high, is a very promising method.SIPM is huge at the sector application potential.
4, substitute the cation-modified terylene blanket of acrylic fiber production process: the acrylic blanket matte is plentiful, feel gentle glutinous, be difficult for advantages such as depilation, heat build-up property are good, favored by the human consumer.But the acrylic fibers raw material is import mostly, and price is higher, causes manufacturing enterprise's profit margin lower.As to select terylene for use be raw material production woollen blanket (coral flannelette blanket), and cost of material is more cheap than acrylic fibers, and have that modulus height, intensity are high, characteristics such as elasticity and model keeping character are good, do not crease easily.In the polymerization process of conventional polyester fiber (PET); Add a small amount of the 3rd component S IPM and the 4th component PEG (polyoxyethylene glycol) makes boiling dyeing at normal pressure type cation-dyeable polyester staple fiber (ECDP), the existence of sulfonic acid group is strengthened the binding ability of itself and dye molecule, and dyeing behavior is improved; Lower like dyeing temperature; Can reduce percent crystallinity simultaneously at normal temperatures and pressures with cationic dyeing or stamp, increase flexibility.At present this technology successfully is applied in the large-scale industry device, has produced remarkable economic efficiency, this will cause the SIPM usage quantity than quantum jump.
Since the last century the nineties; SIPM is more and more in the applied research of above-mentioned industry; Because the difference of target product; Specification of quality to SIPM is not quite similar, and is more and more stricter to this article outward appearance, saponification value, iron ion index requests such as (Fe3+), particularly very harsh to the requirement of sulfone compound, the tetramer etc.If foreign matter content is higher, on the one hand, when SIPM and glycol reaction side reaction many, by product is many, causes last polycondensation product MWD too wide, and numerous side reactions take place generates multiple polycondensation product; On the other hand, in spinning process, no matter be DTY or POY, situation such as fracture of wire, shower nozzle obstruction often appear, influenced the application of spinning process and silk.
In the SIPM synthesis procedure, most critical be the first step sulfonation reaction, research both at home and abroad such as other production process such as esterification, neutralization etc., use and be mature on the whole.Because two carboxyl-COOH are electron-withdrawing group, p-sulfonic acid base-SO in the m-phthalic acid molecular structure
3There is considerable influence the H location, in case material proportion and processing parameter control are improper, and sulfonic group-SO
3H locatees one even a plurality of sulfonic acid group possibly on other position of phenyl ring except location in 5 of the orderings on phenyl ring, or and then polymerization generate the multiple baroque benzene ring compounds that contain such as dipolymer or tetramer.
The synthesis technique of existing SIPM, what industrial applications value was arranged has following several kinds:
1, with the m-phthalic acid is starting raw material, with liquid state or gaseous state SO
3Carry out sulfonation, through over-churning, neutralization, refining and product.
Advantage: adopt sulphur trioxide to make sulphonating agent and do not generate water, speed of response is fast, and active big, waste liquid is few, and the sulphur trioxide consumption can be near theoretical amount, and product yield is high.
But still there is following weak point: when SO 3 sulfonated, very easily form sulfone, cause product purity low.Sometimes need use halogenated alkane to be solvent, or regulate the activity of sulphur trioxide with the mixture of sulphur trioxide and dioxane, pyridine etc.Because SO
3Specific physicochemical property make when producing SIPM equipment material to be required harshness that facility investment is excessive, and production operation is wayward.
2, with the m-phthalic acid be starting raw material, oleum (SO
3Content from 20% to 80% does not wait) for sulphonating agent, obtain product through esterification, neutralization, operation such as refining then.Advantage: along with SO in the oleum
3The raising of content, although the sulfonated product flowability is weaker, reactive behavior improves, and sulfonation reaction speed is fast, and temperature of reaction decreases, and the reaction times shortens, and disulfonic acid thing content is low on the m-phthalic acid; Weak point: no matter adopt still formula process for sulfonation at intermittence still to adopt the continuous process for sulfonation of pot group type, all exist mass transfer poor, it is slow to conduct heat, and is prone to take place local superheating, problems such as side reaction is many, long reaction time, so also cause product purity low.The sodium sulfate that the neutralization back generates is brought in the product, has also influenced product gas purity.
3, generate dimethyl isophthalate with the esterification of m-phthalic acid and methyl alcohol elder generation, mixes the back sulfonation with m-phthalic acid, carry out esterification, neutralization, operation acquisition finished product such as refining again.
This method advantage is: production process is easy to control; Weak point is: technical process is long, and two step esterifications increase side reaction, and product yield is low, and foreign matter content is high in the finished product, and product economy is of poor benefits.This technology is superseded trend.
4, with the m-phthalic acid be starting raw material, chlorsulfonic acid is a sulphonating agent, makes through sulfonation, neutralization, oven dry, esterification, neutralization, operation such as refining.
This method advantage is: the chlorsulfonic acid sulfonation is very capable, is only second to sulphur trioxide, and response capacity is strong, but compares SO
3Gentleness, side reaction is few, generates HCl and is beneficial to reaction, and product purity is high, and useless other technology of acid molar ratio significantly reduces.Weak point is: need twice in the production and add alkali, operational path is long, and product yield is low, and cost is high, and the hydrolysis immediately of chlorsulfonic acid chance water, and harsh to the anhydrous requirement of equipment, facility investment is big, expensive, and HCl has severe corrosive.Need inert solvent (methylene dichloride) existence sometimes and carry out still formula sulfonation reaction with chlorsulfonic acid down.
Existing several kinds of working methods exist all that product purity is low, the high problem of foreign matter content.Therefore, the Application Areas that SIPM is new urgently hopes to have the product that content is high, foreign matter content is low to come out to satisfy different request for utilizations.
Sulfonation reaction is one of typical organic reaction.Multiple Chemicals all will rely on this to react and accomplish.The fundamental research of sulfonation reaction can think at present and be mature on the whole, but from industrialized performance, and it is long also to have many problems, particularly time, and efficient is low.Therefore, strengthen reinforcement research, can bring great economic benefit to enterprise undoubtedly, and have very important learning value it.
(1) sulfonation mechanism
The m-phthalic acid sulfonation reaction belongs to electrophilic substitution reaction on mechanism, when using oleum, electrophilic reagent is that pyrosulfuric acid closes hydrogen ion (being protonated pyrosulfuric acid) and H
2S
4O
13(being a part sulfuric acid+three molecule sulphur trioxides), sulfonation is an electrophilic substitution reaction, SO
3The electronegativity of sulphur atom is littler than the electronegativity of Sauerstoffatom in the molecule, so sulphur atom has the part positive charge and becomes electrophilic reagent.
SO
3H
2SO
4Middle ionization equilibrium is following:
SO
3+H
2SO
4→H
2S
2O
7
H
2S
2O
7+H
2SO
4→H
3SO
4 ++HS
2O
7 -
Influencing m-phthalic acid sulfonated principal element has:
1, the structural group-COOH of m-phthalic acid aromatic hydrocarbons
Be sulfonated structure, the character of thing, the sulfonated complexity is had very big influence.Because of having electron-withdrawing group-COOH on the m-phthalic acid structure, sulfonation is comparatively difficult comparatively speaking.
2, temperature of reaction and time
Enhance productivity, then need shorten the reaction times, guarantee again that simultaneously quality product and productive rate, 10 ℃ of the every increases of the temperature of sulfonation reaction, reaction times shorten to original 1/3.But side reaction also increases when heating up, and quality product will descend.Adopt SO
3Sulfonation then can guarantee at low temperatures, and rapid reaction reduces side reaction with the high yield that guarantees product.
3, sulfonation catalyst and sulfonation auxiliary agent
Add sulfonation catalyst or other auxiliary agents, often reaction is produced significantly influence, its performance has following several respects;
(1) influences the position of substitution, add sulfonation catalyst and can play the localized effect of change.
(2) suppress side reaction, when using oleum to carry out sulfonation, when perhaps concentration and temperature are higher, very easily generate by products such as sulfone as sulphonating agent.The adding auxiliary agent can suppress the generation of sulfone, and some vitriol or benzene sulfonate also have same purpose.The adding catalyzer can stop the generation of oxidation side reaction.
(3) impel reaction to be easy to carry out, add sulfonation catalyst speed of response is accelerated, reaction yield improves, and it is gentle that reaction conditions becomes, sometimes in addition the reaction that some can't be carried out smooth.
When using oleum as sulphonating agent; Because of no moisture in the reaction system exists; Add that three benzene ring substitution groups are electron-withdrawing group on m-phthalic acid-5-sulfonic acid molecular structure, the cloud density on the aromatic ring is lower, and sulfonic acid group can be thought not hydrolysis under the sulfonation condition.
(2) catalyzer is selected
In the prior art, use single catalyst, and the sulfonation reaction temperature is higher, has in various degree that the reaction in early stage is fierce, by product is many and the middle and later periods reactive behavior descends, the m-phthalic acid transformation efficiency improves deficiencies such as slow, directly influenced product yield and quality.
Summary of the invention
Technical problem to be solved by this invention is: to the deficiency that prior art exists, the compound method that a kind of reaction times is short, react dimethyl isophthalate-5-sodium sulfonate that side reaction is few, product purity is high, production cost is low is provided.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The compound method of a kind of dimethyl isophthalate-5-sodium sulfonate; Adopting m-phthalic acid and oleum is raw material; Make through sulfonation reaction, esterification, neutralization reaction and post-processing step; Sulfonation reaction divides three temperature of reaction intervals to carry out, and in the interval different catalyst of using of different temperature of reaction, in the time of 150～159 ℃, uses Cadmium Sulphate to be catalyzer; In the time of 160～169 ℃, use SiO
2Be catalyzer; In the time of 170～181 ℃, use Mercury bisulfate to be catalyzer.
Preferably, said oleum is the oleum of 64～68wt%.
Wherein, During said sulfonation reaction; With the disposable adding sulfonation of said oleum still, whipped state adds 20～30% of m-phthalic acid consumption down, in 20～30 minutes, temperature of charge is brought up to 125～135 ℃; Again remaining m-phthalic acid is all added the sulfonation still, divides following three temperature ranges to carry out then:
When temperature of charge is increased to 150～159 ℃, add Cadmium Sulphate, insulation reaction 60～80 minutes; Temperature of charge is increased to 160～169 ℃ in 30～45 minutes then, and first insulation reaction 20～30 minutes adds SiO
2, insulation reaction is 60～80 minutes again; In 20～50 minutes, temperature of charge is increased to 170～181 ℃ at last, first insulation reaction 30～40 minutes adds Mercury bisulfate, insulation reaction 70～90 minutes.
As a kind of improvement, during said sulfonation reaction, after a benzene disulfonic acid all adds the sulfonation still, add a spot of SODIUM SULPHATE ANHYDROUS 99PCT earlier, add catalyzer again and carry out sulfonation reaction.
As a kind of preferred, reinforced mass ratio is a m-phthalic acid during said sulfonation reaction: oleum: Cadmium Sulphate: SiO
2: Mercury bisulfate: SODIUM SULPHATE ANHYDROUS 99PCT=1: 0.879～0.891: 0.0003～0.001: 0.0005～0.0012: 0.0005～0.0015: 0.001～0.01.
Wherein, the material after the sulfonation reaction was cooled in 1.5～2 hours below 110 ℃, adds 20～30% of methanol usage, treat still temperature drop to 85 ℃ below the back add remaining methyl alcohol, 64～68 ℃ of esterifications of temperature 3～5 hours.
As a kind of preferred, the reinforced mass ratio of methyl alcohol is a m-phthalic acid during said esterification: methyl alcohol=1: 1.05～1.1.
Wherein, the material after the esterification is dissolved in water, the reinforced mass ratio of water is a m-phthalic acid: water=1: 5.35～5.65, be cooled to below 25 ℃, and adding alkali adjusting pH value at 24～28 ℃ is 6.5～7.5, continues to stir 80～120 minutes.
Said aftertreatment comprises centrifuge dehydration, dissolving decolouring, filtration, crystallization and purification and baking step.
As a kind of improvement, when said esterification is dissolved, add the centrifuge mother liquor that centrifuge dehydration is deviate from, the reinforced mass ratio of centrifuge mother liquor is a m-phthalic acid: centrifuge mother liquor=1: 5.35～5.65.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention is when using oleum to carry out sulfonation reaction; Reacting the different of early stage, mid-term and late phase reaction severity according to m-phthalic acid with oleum; Under different step of reaction, different temperature of reaction condition, adopt different catalyst to carry out catalyzed reaction, give full play to the katalysis of catalyzer; Improve the sulfonation reaction effect, therefore improved the transformation efficiency of m-phthalic acid; Reduce the sulfonation reaction temperature and shortened the sulfonation reaction time; And because temperature of reaction is low short with the reaction times, byproduct of reaction two sulfonated bodiess, polymer and sulphones significantly reduce, and have therefore improved product purity, have also improved the yield of product dimethyl isophthalate-5-sodium sulfonate.And because sulfonation is effective; Also greatly reduce the ingredient proportion of a diphenyl disulfide acid and oleum, it is excessive that oleum does not need, and reduced the usage quantity of oleum; Therefore reduced the generation of side reaction in the esterification; Reduced follow-up in operation in the usage quantity of soda ash, thereby reduced production cost, improved productivity effect.
2, the present invention is when sulfonation reaction feeds intake; Add earlier the part m-phthalic acid, insulation reaction heats up after for some time again and adds the residue m-phthalic acid, is adding catalyzer stage by stage when carrying out catalyzed reaction; Also be to heat up again afterreaction for some time first insulation reaction for some time; Reaction control is steadily carried out, and acutely causes the phenomenon that side reaction increases, product purity reduces because of reacting when having avoided one feeding, and has improved production security.
3, the present invention after benzene disulfonic acid all adds the sulfonation still between inciting somebody to action, adds a spot of SODIUM SULPHATE ANHYDROUS 99PCT earlier when sulfonation reaction, carries out sulfonation reaction again, helps reaction and carries out to the title product direction, has reduced the generation of by product sulphones.
4, the present invention is when esterification is dissolved, and the centrifuge mother liquor that uses centrifuge dehydration to deviate from has reduced the usage quantity of water, also the product in the centrifuge mother liquor has been carried out efficient recovery simultaneously.
5, the relative prior art of the present invention; The usage quantity of oleum reduces 20%, and the reaction times shortens more than the nearly 2h, and temperature of reaction reduces by 20 ℃; The yield of 5-sodium sulfo isophthalate improves 2%; Neutralization reduces 10% with the soda ash usage quantity, and the transformation efficiency of m-phthalic acid improves more than 2%, and foreign matter content reduces by 30% than existing technology in the finished product.Production cost descends more than 3%.
Embodiment
Below in conjunction with concrete embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Compound concentration is the oleum of 64wt%, according to m-phthalic acid: oleum: Cadmium Sulphate: SiO
2: Mercury bisulfate: SODIUM SULPHATE ANHYDROUS 99PCT=1: 0.879: 0.0003: 0.0005: 0.0005: 0.001 reinforced mass ratio batching: earlier with the disposable adding sulfonation of oleum still; Open and stir, add 20% of the total consumption of m-phthalic acid, material in the heating sulfonation still; In 20 minutes, temperature of charge is brought up to 125 ℃; Again remaining m-phthalic acid is all added the sulfonation still, add SODIUM SULPHATE ANHYDROUS 99PCT, when then temperature of charge being increased to 150 ℃; Add Cadmium Sulphate, insulation reaction 60 minutes; Temperature of charge is increased to 160 ℃ in 30 minutes then, and first insulation reaction 20 minutes adds SiO
2, insulation reaction is 60 minutes again; In 20 minutes, temperature of charge is increased to 170 ℃ at last, first insulation reaction 30 minutes adds Mercury bisulfate, insulation reaction 70 minutes.
Sulfonation reaction finishes; While hot material in the sulfonation still is put to esterifying kettle; In 1.5 hours,, add 20% of methanol usage, treat to add remaining methyl alcohol behind the still temperature drop to 80 ℃ still temperature drop to 105 ℃; 64 ℃ of esterifications of temperature 3 hours, the reinforced mass ratio of methyl alcohol was a m-phthalic acid: methyl alcohol=1: 1.05.
Material after the esterification is added water, and the reinforced mass ratio of water is a m-phthalic acid: water=1: 5.35, be cooled to 25 ℃, and controlled temperature is 25 ℃, adding alkali adjusting pH value is 7, stops to add alkali, continues to stir 20 minutes, after the pH value is 6.5, continues to stir 80 minutes.
Material after neutralization reaction finishes makes finished product through centrifuge dehydration, dissolving decolouring, filtration, crystallization and purification and baking step.
Embodiment 2
Compound concentration is the oleum of 65wt%, according to m-phthalic acid: oleum: Cadmium Sulphate: SiO
2: Mercury bisulfate: SODIUM SULPHATE ANHYDROUS 99PCT=1: 0.885: 0.0006: 0.0009: 0.0009: 0.004 reinforced mass ratio batching: earlier with the disposable adding sulfonation of oleum still; Open and stir, add 24% of the total consumption of m-phthalic acid, material in the heating sulfonation still; In 24 minutes, temperature of charge is brought up to 128 ℃; Again remaining m-phthalic acid is all added the sulfonation still, add a spot of SODIUM SULPHATE ANHYDROUS 99PCT, when then temperature of charge being increased to 153 ℃; Add Cadmium Sulphate, insulation reaction 70 minutes; Temperature of charge is increased to 163 ℃ in 35 minutes then, and first insulation reaction 24 minutes adds SiO
2, insulation reaction is 68 minutes again; In 30 minutes, temperature of charge is increased to 173 ℃ at last, first insulation reaction 35 minutes adds Mercury bisulfate, insulation reaction 80 minutes.
Sulfonation reaction finishes; While hot material in the sulfonation still is put to esterifying kettle; In 1.8 hours,, add 24% of methanol usage, treat to add remaining methyl alcohol behind the still temperature drop to 83 ℃ still temperature drop to 108 ℃; 65 ℃ of esterifications of temperature 3.5 hours, the reinforced mass ratio of methyl alcohol was a m-phthalic acid: methyl alcohol=1: 1.07.
Material after the esterification is added the centrifuge mother liquor dissolving that centrifuge dehydration is deviate from, and the reinforced mass ratio of centrifuge mother liquor is a m-phthalic acid: centrifuge mother liquor=1: 5.45 is cooled to 26 ℃; Controlled temperature is 26 ℃; Adding alkali adjusting pH value is 7, stops to add alkali, continues to stir 25 minutes; After the pH value is 7.0, continue to stir 90 minutes.
Material after neutralization reaction finishes makes finished product through centrifuge dehydration, dissolving decolouring, filtration, crystallization and purification and baking step.
Embodiment 3
Compound concentration is the oleum of 66wt%, according to m-phthalic acid: oleum: Cadmium Sulphate: SiO
2: Mercury bisulfate: SODIUM SULPHATE ANHYDROUS 99PCT=1: 0.889: 0.0008: 0.0010: 0.0012: 0.008 reinforced mass ratio batching: earlier with the disposable adding sulfonation of oleum still, open and stir, add 26% of the total consumption of m-phthalic acid; Material in the heating sulfonation still; In 28 minutes, temperature of charge is brought up to 130 ℃, more remaining m-phthalic acid is all added the sulfonation still, when then temperature of charge being increased to 156 ℃; Add Cadmium Sulphate, insulation reaction 70 minutes; Temperature of charge is increased to 166 ℃ in 40 minutes then, and first insulation reaction 28 minutes adds SiO
2, insulation reaction is 75 minutes again; In 40 minutes, temperature of charge is increased to 176 ℃ at last, first insulation reaction 36 minutes adds Mercury bisulfate, insulation reaction 80 minutes.
Sulfonation reaction finishes; While hot material in the sulfonation still is put to esterifying kettle; In 1.8 hours,, add 28% of methanol usage, treat to add remaining methyl alcohol behind the still temperature drop to 85 ℃ still temperature drop to 108 ℃; 67 ℃ of esterifications of temperature 4 hours, the reinforced mass ratio of methyl alcohol was a m-phthalic acid: methyl alcohol=1: 1.09.
Material after the esterification is added the centrifuge mother liquor dissolving that centrifuge dehydration is deviate from, and the reinforced mass ratio of centrifuge mother liquor is a m-phthalic acid: centrifuge mother liquor=1: 5.55 is cooled to below 25 ℃; Controlled temperature is 26 ℃; Adding alkali adjusting pH value is 7.5, stops to add alkali, continues to stir 30 minutes; After the pH value is 7.5, continue to stir 110 minutes.
Material after neutralization reaction finishes makes finished product through centrifuge dehydration, dissolving decolouring, filtration, crystallization and purification and baking step.
Embodiment 4
Compound concentration is the oleum of 68wt%, according to m-phthalic acid: oleum: Cadmium Sulphate: SiO
2: Mercury bisulfate: SODIUM SULPHATE ANHYDROUS 99PCT=1: 0.891: 0.001: 0.0012: 0.0015: 0.01 reinforced mass ratio batching: earlier with the disposable adding sulfonation of oleum still; Open and stir, add 30% of the total consumption of m-phthalic acid, material in the heating sulfonation still; In 30 minutes, temperature of charge is brought up to 135 ℃; Again remaining m-phthalic acid is all added the sulfonation still, add a spot of SODIUM SULPHATE ANHYDROUS 99PCT, when then temperature of charge being increased to 159 ℃; Add Cadmium Sulphate, insulation reaction 80 minutes; Temperature of charge is increased to 169 ℃ in 45 minutes then, and first insulation reaction 30 minutes adds SiO
2, insulation reaction is 80 minutes again; In 50 minutes, temperature of charge is increased to 181 ℃ at last, first insulation reaction 40 minutes adds Mercury bisulfate, insulation reaction 85 minutes.
Sulfonation reaction finishes; While hot material in the sulfonation still is put to esterifying kettle; In 2 hours,, add 30% of methanol usage with still temperature drop to 105 ℃, treat still temperature drop to 85 ℃ below the back add remaining methyl alcohol; 68 ℃ of esterifications of temperature 5 hours, the reinforced mass ratio of methyl alcohol was a m-phthalic acid: methyl alcohol=1: 1.1.
Material after the esterification is dissolved in water, and the reinforced mass ratio of water is a m-phthalic acid: water=1: 5.65 is cooled to below 25 ℃; Controlled temperature is 28 ℃, and adding alkali adjusting pH value is 7.5, stops to add alkali; Continue to stir 20 minutes, after the pH value is 7.5, continue to stir 120 minutes.
Material after neutralization reaction finishes makes finished product through centrifuge dehydration, dissolving decolouring, filtration, crystallization and purification and baking step.
The product quality indicator for preparing among each embodiment is seen table 1.
Table 1
Claims (10)
1. the compound method of dimethyl isophthalate-5-sodium sulfonate; Adopting m-phthalic acid and oleum is raw material; Make through sulfonation reaction, esterification, neutralization reaction and post-processing step; It is characterized in that: sulfonation reaction divides three temperature of reaction intervals to carry out, and in the interval different catalyst of using of different temperature of reaction, in the time of 150～159 ℃, uses Cadmium Sulphate to be catalyzer; In the time of 160～169 ℃, use SiO
2Be catalyzer; In the time of 170～181 ℃, use Mercury bisulfate to be catalyzer.
2. the compound method of dimethyl isophthalate as claimed in claim 1-5-sodium sulfonate is characterized in that: said oleum is the oleum of 64～68wt%.
3. the compound method of dimethyl isophthalate as claimed in claim 1-5-sodium sulfonate; When it is characterized in that said sulfonation reaction; With the disposable adding sulfonation of said oleum still, whipped state adds 20～30% of m-phthalic acid consumption down, in 20～30 minutes, temperature of charge is brought up to 125～135 ℃; Again remaining m-phthalic acid is all added the sulfonation still, divides following three temperature ranges to carry out then:
When temperature of charge is increased to 150～159 ℃, add Cadmium Sulphate, insulation reaction 60～80 minutes; Temperature of charge is increased to 160～169 ℃ in 30～45 minutes then, and first insulation reaction 20～30 minutes adds SiO
2, insulation reaction is 60～80 minutes again; In 20～50 minutes, temperature of charge is increased to 170～181 ℃ at last, first insulation reaction 30～40 minutes adds Mercury bisulfate, insulation reaction 70～90 minutes.
4. the compound method of dimethyl isophthalate as claimed in claim 3-5-sodium sulfonate when it is characterized in that said sulfonation reaction, after a benzene disulfonic acid all adds the sulfonation still, adds a spot of SODIUM SULPHATE ANHYDROUS 99PCT earlier, adds catalyzer again and carries out sulfonation reaction.
5. the compound method of dimethyl isophthalate as claimed in claim 4-5-sodium sulfonate is characterized in that: reinforced mass ratio is a m-phthalic acid during said sulfonation reaction: oleum: Cadmium Sulphate: SiO
2: Mercury bisulfate: SODIUM SULPHATE ANHYDROUS 99PCT=1: 0.879～0.891: 0.0003～0.001: 0.0005～0.0012: 0.0005～0.0015: 0.001～0.01.
6. the compound method of dimethyl isophthalate as claimed in claim 1-5-sodium sulfonate; It is characterized in that: in 1.5～2 hours, be cooled to the material after the sulfonation reaction below 110 ℃; Add 20～30% of methanol usage; Treat that the back adds remaining methyl alcohol below the still temperature drop to 85 ℃, 64～68 ℃ of esterifications of temperature 3～5 hours.
7. the compound method of dimethyl isophthalate as claimed in claim 6-5-sodium sulfonate is characterized in that: the reinforced mass ratio of methyl alcohol is a m-phthalic acid during said esterification: methyl alcohol=1: 1.05～1.1.
8. the compound method of dimethyl isophthalate as claimed in claim 1-5-sodium sulfonate; It is characterized in that: the material after the esterification is dissolved in water; The reinforced mass ratio of water is a m-phthalic acid: water=1: 5.35～5.65; Be cooled to below 25 ℃, adding alkali adjusting pH value at 24～28 ℃ is 6.5～7.5, continues to stir 80～120 minutes.
9. the compound method of dimethyl isophthalate as claimed in claim 1-5-sodium sulfonate is characterized in that: said aftertreatment comprises centrifuge dehydration, dissolving decolouring, filtration, crystallization and purification and baking step.
10. the compound method of dimethyl isophthalate as claimed in claim 9-5-sodium sulfonate; It is characterized in that: when said esterification is dissolved; Add the centrifuge mother liquor that centrifuge dehydration is deviate from, the reinforced mass ratio of centrifuge mother liquor is a m-phthalic acid: centrifuge mother liquor=1: 5.35～5.65.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242205A (en) * | 2013-05-17 | 2013-08-14 | 潍坊沃尔特化学有限公司 | Tri-monomer preparation method capable of reducing waste water production |
| CN105541675A (en) * | 2015-12-24 | 2016-05-04 | 宜兴市顺发化工有限公司 | Preparing method of dioctyl terephthalate |
| CN106066371A (en) * | 2015-04-09 | 2016-11-02 | 青岛中科荣达新材料有限公司 | A kind of three monomer liquid chromatograph rapid analysis methods |
| CN107827788A (en) * | 2017-11-21 | 2018-03-23 | 赞宇科技集团股份有限公司 | A kind of production technology of high-quality alkyl benzene sulphonate |
| CN108752242A (en) * | 2018-06-28 | 2018-11-06 | 金华双宏化工有限公司 | For the method for sulfonating of low cloud density aromatic hydrocarbons |
| CN109020840A (en) * | 2018-09-19 | 2018-12-18 | 青岛中科荣达新材料有限公司 | A kind of production method improving M-phthalic acid -5- sulfonic acid yield |
| CN109180538A (en) * | 2018-09-19 | 2019-01-11 | 泰山医学院 | A kind of production method for improving the synthesis of three monomers and using M-phthalic acid -5- sulfonic acid yield |
| CN109608366A (en) * | 2018-12-18 | 2019-04-12 | 泰山医学院 | A kind of production method for improving the synthesis of three monomers and using dimethyl isophthalate -5- sulfonic acid yield and purity |
| CN110252396A (en) * | 2019-06-27 | 2019-09-20 | 山东第一医科大学(山东省医学科学院) | A kind of catalyst in Sodium Dimethyl Isophthalate-5-sulfonate synthesis process, preparation method and application |
| CN110302793A (en) * | 2019-07-08 | 2019-10-08 | 山东第一医科大学(山东省医学科学院) | A kind of Sodium Dimethyl Isophthalate-5-sulfonate catalyst for synthesizing and its application |
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| CN106066371B (en) * | 2015-04-09 | 2018-07-06 | 青岛中科荣达新材料有限公司 | A kind of three monomer liquid chromatogram rapid analysis methods |
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| CN109180538B (en) * | 2018-09-19 | 2021-04-16 | 山东第一医科大学(山东省医学科学院) | Production method for improving yield of m-phthalic acid-5-sulfonic acid for synthesizing three monomers |
| CN109608366A (en) * | 2018-12-18 | 2019-04-12 | 泰山医学院 | A kind of production method for improving the synthesis of three monomers and using dimethyl isophthalate -5- sulfonic acid yield and purity |
| CN109608366B (en) * | 2018-12-18 | 2021-06-22 | 山东第一医科大学(山东省医学科学院) | Production method for improving yield and purity of m-phthalic acid dimethyl ester-5-sulfonic acid for three-monomer synthesis |
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| CN110302793B (en) * | 2019-07-08 | 2022-04-15 | 山东第一医科大学(山东省医学科学院) | Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate and application thereof |
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