CN1304684C - Synthesis technology of polyester dying modifier SIPM - Google Patents
Synthesis technology of polyester dying modifier SIPM Download PDFInfo
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- CN1304684C CN1304684C CNB2005100379767A CN200510037976A CN1304684C CN 1304684 C CN1304684 C CN 1304684C CN B2005100379767 A CNB2005100379767 A CN B2005100379767A CN 200510037976 A CN200510037976 A CN 200510037976A CN 1304684 C CN1304684 C CN 1304684C
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- salify
- sipm
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Abstract
The present invention discloses a synthesis technology of polyester dyeing modifiers SIPM, which relates to an industrial production technology of a chemical product, particularly to a production technology of polyester dyeing modifier third monomers. Isophthalic acid is sulfonated and then is treated through the esterification, the salt forming, the purification and the recrystallization, and is dried to obtain finished goods, wherein oleum, the concentration of free SO3<-> of which is from 30 to 50%, is sulfonated at the temperature of 170 to 200 DEG C. The present invention adopts medium concentration oleum, the concentration of free SO3<-> of which is from 30 to 50%, and the oleum is sulfonated at the temperature of 170 to 200 DEG C. Compared with the sulfonation of low concentration and high concentration oleum, the present invention has the advantages of high product yield and good quality, and lays the foundation for acid salt forming.
Description
Technical field:
The present invention relates to a kind of industrial manufacture process of chemical products, particularly the production technology of estrodur dyeing modifier the 3rd monomer.
Background technology:
Polyester fiber has become global first chemical fiber plus material fiber because of it is good and cheap, but its dyeing difficulty has restricted its development again, and the preparation cation dyeable polyester is the optimal path that solves colouring problem.Polyester dyeing modified SIPM claims polyester the 3rd monomer again, is first-selected estrodur dyeing modifier, because it has active sulfonic acid group, behind polyethylene terephthalate copolymer, has increased the compatibility of polyester to dyestuff, and absorption of perspiration and the gas permeability to fiber also increases simultaneously.Polyester dyeing modified SIPM has at home and abroad been produced for many years, and multiple synthetic route is arranged, and world's main flow synthesis route is at present: with M-phthalic acid (being called for short IPA) earlier sulfonation, and esterification then, salify, refining, recrystallization, oven dry at last obtains finished product.
First three step is synthesis route, wherein the general SO that dissociates that adopts of sulfonation
3 -Concentration is 20～23% low concentration fuming sulphuric acid or free SO
3 -Concentration is high concentration fuming sulfuric acid and three kinds of concentration sulfonation of sulfur trioxide method of 65～67%, produces waste water thus and how much differ after course of reaction.In addition, in all bibliographical informations, all adopt NaOH or Na
2CO
3The gap salify becomes salting liquid to neutrality or subacidity (pH value is 5～7), does not see continuous salify report.After reaction finishes, all adopt still formula gap refining and since the gap when refining the hot situation time longer, so the product hydrolysis phenomenon is more serious.
Salify waste water is used alkali (NaOH, Na after generally reclaiming methyl alcohol in the traditional handicraft
2CO
3) the neutralization discharging, COD content height in the waste water, and need to consume a large amount of alkali, thereby processing cost is higher.At present existing production technology product yield level is generally between 60～75%.
The utility model purpose is to invent a kind of SIPM production technology of serialization, and it is low to have a production cost, product yield height, characteristics such as energy consumption is low.
Process of the present invention is: with the M-phthalic acid earlier sulfonation, and esterification then, salify, refining, recrystallization, oven dry at last obtains finished product, is characterized in adopting free SO
3 -Concentration is 30～50% fuming sulphuric acids, carries out sulfonation under 170～200 ℃ of temperature.
The present invention adopts free SO
3 -Concentration is 30～50% middle concentration fuming sulphuric acid, carries out sulfonation under 170～200 ℃ of temperature, low concentration with the high concentration fuming acid sulfonation compare, product yield is higher, quality is better, lays the foundation for realizing acid salify.
The domestic and foreign literature report, neutral salt forming method is all adopted in three monomer productions, adopts NaOH or sodium carbonate salify, and salify later stage PH transfers to neutrality (PH=5-7).Technical process of the present invention realizes acid salify, promptly use NaOH, sodium carbonate or salifies such as sodium sulphate, sodium chloride, its salify later stage acidity is controlled at 1～10%, the product yield of acid salify is generally high by 3～5% than neutral salify, and behind the salify in the crude product sodium sulphate (sodium chloride) etc. carry secretly few, the crude product quality increases, and has reduced refining difficulty.
About the reported in literature salify all adopts in the still formula gap and salify, regulate PH to neutral.The present invention adopts the continous mode salify, and system is acid (acidity 1～10%), and soon esterifying liquid, refining crystallization separate freezing mother liquor and inorganic base or inorganic sodium and mix salify according to a certain ratio continuously in a container, and realize that continuous filter press separates.This technology can be guaranteed in the crude product wrapped folder sodium sulphate or sodium chloride as few as possible, improves product yield.
Because the aqueous solution (more than 60 ℃) hydrolysis at high temperature of three monomers is serious, thus when refining behind the length of heating rate and subtractive process and the refining impurity screening rate of temperature fall directly have influence on the product hydrolysis degree, and then influence the yield and the quality of product.Continuous treating and dynamic crystallization are based in improvement of the present invention, promptly strive finishing in the shortest time refining, removal of impurities and crystallization process, to guarantee product quality and yield.Concrete technology is for to put into crude product after the salify press filtration by a certain percentage in the refinement mother liquor of precooling, regulate PH to 5.5～6.5, making beating and the muddy liquid of crude product that regulates PH are squeezed in the heat exchanger with pump, by regulating flow, be settled solution to guarantee that the crude product turbid solution dissolves rapidly behind heat exchanger, squeeze in the refining kettle, add a certain amount of activated carbon removal of impurities decolouring, and it is removed impurity such as activated carbon by the PA accurate filter fast with pump, enter in the dynamic crystallization device crystallisation by cooling rapidly.This process modification is owing to adopt continuous treating, and the dynamic crystallization technology makes product quality better, and three monomer solutions are shorter in the following time of hot state, and the yield level is refining high by 2～3% than the gap.
In sum, because concentration acid (30～50% fuming sulphuric acid) sulfonation during the present invention adopts, acid salify (acidity is 1～10% during salify), continuous salify, continuous treating and dynamic crystallization technology, product yield are up to 78～82%, and product quality reaches industry top grade standard, productivity effect is greatly improved, and great contribution is made in actual production.
Specific embodiment:
Example one:
1, concentration H in the preparation
2SO
4SO
3:
With the free SO of 149kg
3 -Concentration is 20% fuming sulphuric acid and the free SO of 43kg
3 -Concentration is that 65% fuming sulphuric acid is fully mixed, stand-by.
2, sulfonating reaction:
IPA: middle concentration H
2SO
4SO
3=1: 1～2, under 180～190 ℃ of temperature, reacted 4～8 hours, until sulphonation rate 〉=99%.
3, esterification:
The sulfonation material put to esterifying kettle be cooled to below 100 ℃, drip 100～200kg methyl alcohol, 60～90 ℃ of holding temperatures, 2～4 hours reaction time, esterification yield 〉=95%.
4, neutralization is saltoutd:
The esterification gob added in 1～4 times the refinement mother liquor water, temperature is reduced to below 30 ℃, drip 30% liquid caustic soda (or inorganic sodium), acidity is 1～10% behind the salify, can realize continuous salify.(if using still formula salify, 0.5～2 hour reaction time)
5, refining:
1 part of salify filter cake adds 2～5 parts of deionized waters (or recrystallization mother liquor water), under 80～100 ℃, dissolves through strong heat exchanger (or still formula gap), and adsorbs and secondary filter through decolorizing with activated carbon, product is made with extra care (regulated PH to 6～7, add an amount of H
2O
2, AC etc.)
6, crystallization:
To make with extra care filtrate continuous crystallisation in 1000～10000L glassed steel reaction vessels, when feed temperature is reduced to about 60 ℃, regulate speed of agitator to 10～40 rev/min, to guarantee that the crystallization nucleus forms, and keep the quiet hour more than 2 hours, guarantee growing up of crystal, last crystallization material is reduced to room temperature and is separated in order to dehydration.
7, finished product:
Obtain 142.5kg polyester dyeing modified SIPM crystalline product at last.
Example two:
1, concentration H in the preparation
2SO
4SO
3: with the free SO of 48kg
3 -Concentration is 20% fuming sulphuric acid and the free SO of 96kg
3 -Concentration is that 65% fuming sulphuric acid is fully mixed, stand-by.
2, sulfonating reaction:
IPA: middle concentration H
2SO
4SO
3=1: 1～2, under 170～185 ℃ of temperature, reacted 4～8 hours, until sulphonation rate 〉=99%
3, esterification:
The sulfonation material put to esterifying kettle be cooled to below 100 ℃, drip 100～200kg methyl alcohol, 60～90 ℃ of holding temperatures, 2～4 hours reaction time, esterification yield 〉=95%.
4, neutralization is saltoutd:
The esterification gob added in 1～4 times the refinement mother liquor water, temperature is reduced to below 30 ℃, drip 30% liquid caustic soda (or inorganic sodium), acidity is 1～10% behind the salify, can realize continuous salify.(if using still formula salify, 0.5～2 hour reaction time)
5, refining:
1 part of salify filter cake adds 2～5 parts of deionized waters (or recrystallization mother liquor water), under 80～100 ℃, dissolves through strong heat exchanger (or still formula gap), and adsorbs and secondary filter through decolorizing with activated carbon, product is made with extra care (regulated PH to 6～7, add an amount of H
2O
2, AC etc.)
6, crystallization:
To make with extra care filtrate continuous crystallisation in 1000～10000L glassed steel reaction vessels, when feed temperature is reduced to about 60 ℃, regulate speed of agitator to 10～40 rev/min, to guarantee that the crystallization nucleus forms, and keep the quiet hour more than 2 hours, guarantee growing up of crystal, last crystallization material is reduced to room temperature and is separated in order to dehydration.
7, finished product:
Obtain 142.5kg polyester dyeing modified SIPM crystalline product at last.
Claims (3)
1, synthesis technology of polyester dying modifier SIPM, comprise that adopting free SO3-concentration is that 30～50% fuming sulphuric acids are under 170～200 ℃ of temperature, with the M-phthalic acid earlier sulfonation, esterification then, salify, refining, recrystallization, oven dry at last obtains finished product, it is characterized in that salify later stage acidity is controlled at 1～10%.
2, according to the described synthesis technology of polyester dying modifier SIPM of claim 1, it is characterized in that adopting continuous treating, dynamic crystallization.
3, according to the described synthesis technology of polyester dying modifier SIPM of claim 2, it is characterized in that crude product after the salify press filtration is put in the refinement mother liquor of precooling by a certain percentage, regulate PH to 5.5～6.5, making beating and the muddy liquid of crude product that regulates PH are squeezed in the heat exchanger with pump, by regulating flow, be settled solution to guarantee that the crude product turbid solution dissolves rapidly behind heat exchanger, squeeze in the refining kettle, add a certain amount of activated carbon removal of impurities decolouring, and it is removed impurity by the PA accurate filter fast with pump, enter in the dynamic crystallization device crystallisation by cooling rapidly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100379767A CN1304684C (en) | 2005-03-07 | 2005-03-07 | Synthesis technology of polyester dying modifier SIPM |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100379767A CN1304684C (en) | 2005-03-07 | 2005-03-07 | Synthesis technology of polyester dying modifier SIPM |
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| Publication Number | Publication Date |
|---|---|
| CN1673450A CN1673450A (en) | 2005-09-28 |
| CN1304684C true CN1304684C (en) | 2007-03-14 |
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|---|---|---|---|
| CNB2005100379767A Expired - Fee Related CN1304684C (en) | 2005-03-07 | 2005-03-07 | Synthesis technology of polyester dying modifier SIPM |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010099532A2 (en) | 2009-02-27 | 2010-09-02 | Futurefuel Chemical Company | Purification of 5-sulfoisophthalic acid by the use of an acetic acid wash on a crude cake |
| US9359292B2 (en) | 2009-10-20 | 2016-06-07 | Futurefuel Chemical Company | Use of an acetic acid/water solvent mixture for the preparation of low-sulfate 5-sulfoisophthalic acid, mono-lithium salt from 5-sulfoisophthalic acid |
| US8884045B2 (en) | 2010-10-19 | 2014-11-11 | Future Fuel Chemical Company | Use of an acetic acid wash to prepare low-sulfate 5-sulfoisophthalic acid, mono-lithium salt |
| JP2014508163A (en) | 2011-03-02 | 2014-04-03 | フューチャーフューエル ケミカル カンパニー | Metal salt of dialkyl ester of 5-sulfoisophthalic acid and preparation method thereof |
| US8809565B2 (en) | 2011-08-29 | 2014-08-19 | Futurefuel Chemical Company | 5-sulfoisophthalic acid salts and process for the preparation thereof |
| CN102617413B (en) * | 2012-03-20 | 2014-03-19 | 山东旭业新材料股份有限公司 | Method for preparing sodium dimethyl isophthalate-5-sulfonate from high-concentration fuming sulfuric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1203909A (en) * | 1997-06-28 | 1999-01-06 | 天津石油化工公司研究所 | Method for preparing 3,5-phthalic dimethyl ester sulfonate sodium |
| CN1464131A (en) * | 2002-06-13 | 2003-12-31 | 中国石化上海石油化工股份有限公司 | Process for manufacturing coloration additive for producing positive ionic dye dyeable polypropylene |
-
2005
- 2005-03-07 CN CNB2005100379767A patent/CN1304684C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1203909A (en) * | 1997-06-28 | 1999-01-06 | 天津石油化工公司研究所 | Method for preparing 3,5-phthalic dimethyl ester sulfonate sodium |
| CN1464131A (en) * | 2002-06-13 | 2003-12-31 | 中国石化上海石油化工股份有限公司 | Process for manufacturing coloration additive for producing positive ionic dye dyeable polypropylene |
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| CN1673450A (en) | 2005-09-28 |
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