CN109320440A - A method of synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate - Google Patents
A method of synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate Download PDFInfo
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- CN109320440A CN109320440A CN201811381327.2A CN201811381327A CN109320440A CN 109320440 A CN109320440 A CN 109320440A CN 201811381327 A CN201811381327 A CN 201811381327A CN 109320440 A CN109320440 A CN 109320440A
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- Prior art keywords
- sodium
- sulfonate
- phthalic acid
- synthesis
- binaryglycol ester
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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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
Abstract
This application involves a kind of methods for synthesizing M-phthalic acid binaryglycol ester -5- sodium sulfonate, the method includes there are carbon monoxide-olefin polymeric, and under the reaction temperature less than or equal to 185 DEG C, react Sodium Dimethyl Isophthalate-5-sulfonate under an inert atmosphere with ethylene glycol；Wherein the carbon monoxide-olefin polymeric includes at least one alkali metal acylate and at least one alkaline-earth metal acylate.The beneficial effects of the present application are as follows passing through the type and dosage that adjust used catalyst in Sodium Dimethyl Isophthalate-5-sulfonate and glycol ester exchange reaction, the ester exchange rate of Sodium Dimethyl Isophthalate-5-sulfonate can be significantly improved, while reducing the content of diethylene glycol in gained M-phthalic acid binaryglycol ester -5- sodium sulfonate.
Description
Technical field
This application involves estrodur dyeing modifier technical fields.Specifically, this application involves a kind of synthesis isophthalic diformazans
The method of acid diethylene glycol ester -5- sodium sulfonate.
Background technique
M-phthalic acid binaryglycol ester -5- sodium sulfonate (also known as 1,3- phthalic acid binaryglycol ester -5- sodium sulfonate, under
Text is referred to as SIPE) it is a kind of very important industrial chemicals, the dyeability of polyester dacron can be improved, especially in normal pressure type
It is widely used in the synthesis process of cation dyeable polyester and high-temp and-pressure cation dyeable polyester.
Currently, the technique for preparing M-phthalic acid binaryglycol ester -5- sodium sulfonate is usual, there are two types of techniques.The first technique
It is to make 5-sodium sulfo isophthalate and glycol reaction, M-phthalic acid binaryglycol ester -5- is synthesized by direct esterification
Sodium sulfonate.It is entitled " M-phthalic acid binaryglycol ester -5- sulfonic acid to be prepared with M-phthalic acid -5- sulfonate direct esterification
Sodium " Chinese invention patent application 200710008698.1 discloses a kind of direct esterification to prepare M-phthalic acid diethylene glycol
The method of ester -5- sodium sulfonate, but the water generated in esterification process will affect the activity of traditional catalyst, and urge after reaction
Agent is difficult to separate from product because product can be dissolved in, to influence M-phthalic acid binaryglycol ester -5- sodium sulfonate work
The dyeability of polyester synthesis is participated in for Third monomer.
Second of technique is to make Sodium Dimethyl Isophthalate-5-sulfonate (also known as 1,3- rutgers -5- sulfonic acid
Sodium, hereinafter referred SIPM) ester exchange reaction is carried out with ethylene glycol prepares M-phthalic acid binaryglycol ester -5- sodium sulfonate.?
It is prosperous flood paper " preparation and application of polyester modification Third monomer solution " (" polyester industrial ", 2001, the 1st phase of volume 14,42-
46) method for preparing M-phthalic acid binaryglycol ester -5- sodium sulfonate is disclosed through transesterification in.The deficiency of the technique
Place is that while to joined anti-dose of ether, but the diethylene glycol content in products obtained therefrom solution is still higher, and diethylene glycol can shadow
The fusing point of polyester fiber is rung, and influences the heat-resisting of polyester fiber, light fastness and dyeability.
Although inflammable by-product first can be generated by preparing M-phthalic acid binaryglycol ester -5- sodium sulfonate by ester-interchange method
Alcohol brings challenges to equipment and operating environment, but overall cost is lower.For this purpose, there is still a need for continually develop a kind of ester friendship for this field
The method for changing the synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate that rate is high and diethylene glycol content is low.
Summary of the invention
The application's is designed to provide the synthesis M-phthalic acid two that a kind of ester exchange rate is high and diethylene glycol content is low
The method of glycol ester -5- sodium sulfonate, thus solve it is above-mentioned in the prior art the technical issues of.After the application by testing repeatedly
It is surprisingly found that by adjusting used catalyst in Sodium Dimethyl Isophthalate-5-sulfonate and glycol ester exchange reaction
Type and dosage, the ester exchange rate of Sodium Dimethyl Isophthalate-5-sulfonate can be significantly improved, at the same reduce gained isophthalic
The content of diethylene glycol (DEG) in dicarboxylic diol ester -5- sodium sulfonate.
To achieve the goals above, the application provides following technical proposals.
In the first aspect, the application provides a kind of method for synthesizing M-phthalic acid binaryglycol ester -5- sodium sulfonate, institute
The method of stating is included in there are in the case where carbon monoxide-olefin polymeric, and under the reaction temperature less than or equal to 185 DEG C, makes isophthalic two
Formic acid dimethyl ester -5- sodium sulfonate reacts under an inert atmosphere with ethylene glycol；Wherein the carbon monoxide-olefin polymeric includes at least one
Alkali metal acylate and at least one alkaline-earth metal acylate.
In a kind of embodiment of first aspect, the alkali metal acylate includes sodium acetate, and the alkaline earth is golden
Belonging to acylate includes calcium acetate.
In a kind of embodiment of first aspect, the alkali metal acylate includes sodium acetate, and the alkaline earth is golden
Belonging to acylate includes calcium acetate, and the carbon monoxide-olefin polymeric further includes nickel acetate.
It in a kind of embodiment of first aspect, is counted on the basis of quality, the dosage of sodium acetate is M-phthalic acid two
The 0.05%-0.1% of methyl esters -5- sodium sulfonate dosage.
It in a kind of embodiment of first aspect, is counted on the basis of quality, the dosage of calcium acetate is M-phthalic acid two
The 0.15%-0.3% of methyl esters -5- sodium sulfonate dosage.
It in a kind of embodiment of first aspect, is counted on the basis of quality, the dosage of nickel acetate is M-phthalic acid two
The 0.02%-0.12% of methyl esters -5- sodium sulfonate dosage.
It in a kind of embodiment of first aspect, is counted on the basis of molal quantity, ethylene glycol is relative to M-phthalic acid two
The usage ratio of methyl esters -5- sodium sulfonate is greater than 2:1.
In a kind of embodiment of first aspect, the reaction temperature is 130 DEG C -185 DEG C.
In a kind of embodiment of first aspect, when adding catalyst into reaction mass, whole vinegar is first added
The sodium acetate of sour calcium and first part after reacting and carrying out predetermined amount of time, then adds the sodium acetate and nickel acetate of remainder.
Compared with prior art, the beneficial effects of the present application are as follows by adjusting Sodium Dimethyl Isophthalate-5-sulfonate
With the type and dosage of catalyst used in glycol ester exchange reaction, dimethyl isophthalate -5- can be significantly improved
The ester exchange rate of sodium sulfonate, while reducing the content of DEG in gained M-phthalic acid binaryglycol ester -5- sodium sulfonate.
Specific embodiment
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
Embodiment
Below in conjunction with the embodiment of the present invention, clear and complete description is carried out to technical solution of the present invention.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.
Synthetic example
Embodiment 1
The ethylene glycol of the dimethyl isophthalate of 500kg and 1250kg are put into reaction kettle, blender is started, is added
The sodium acetate of 0.25kg and the calcium acetate of 0.75kg close feeding port, are passed through nitrogen protection, start heater, will in 2 hours
Material is heated to 185 DEG C from room temperature.After reaction about 4-6 hours, stops reaction, obtain the binaryglycol ester containing M-phthalic acid
Reaction product.Reaction product is cooled to 130 DEG C hereinafter, and characterizing its every physical and chemical performance, the table 1 that as a result see below.
Embodiment 2
The ethylene glycol of the dimethyl isophthalate of 500kg and 1250kg are put into reaction kettle, blender is started, is added
The sodium acetate of 0.5kg and the calcium acetate of 1.5kg close feeding port, are passed through nitrogen protection, start heater, by object in 2 hours
Material is heated to 185 DEG C from room temperature.After reaction about 4-6 hours, stops reaction, obtain the anti-of the binaryglycol ester containing M-phthalic acid
Answer product.Reaction product is cooled to 130 DEG C hereinafter, and characterizing its every physical and chemical performance, the table 1 that as a result see below.
Embodiment 3
The ethylene glycol of the dimethyl isophthalate of 500kg and 1250kg are put into reaction kettle, blender is started, is added
The nickel acetate of the sodium acetate of 0.25kg, the calcium acetate of 0.75kg and 0.6kg closes feeding port, is passed through nitrogen protection, starting heating
Material was heated to 185 DEG C from room temperature in 2 hours by device.After reaction about 4-6 hours, stops reaction, obtain diformazan containing isophthalic
The reaction product of acid diethylene glycol ester.By reaction product be cooled to 130 DEG C hereinafter, and characterize its every physical and chemical performance, as a result join
The table 1 to see below.
Embodiment 4
The ethylene glycol of the dimethyl isophthalate of 500kg and 1250kg are put into reaction kettle, blender is started, is added
The sodium acetate of 0.15kg and the calcium acetate of 0.75kg close feeding port, are passed through nitrogen protection, start heater, will in 2 hours
Material is heated to 185 DEG C from room temperature.After reaction about 2 hours, stop reaction.Then the vinegar of 0.10kg is added into reaction kettle again
The nickel acetate of sour sodium and 0.1kg, the reaction was continued 3-4 hours, obtains the reaction product of the binaryglycol ester containing M-phthalic acid.It will be anti-
Product is answered to be cooled to 130 DEG C hereinafter, and characterizing its every physical and chemical performance, the table 1 that as a result see below.
Table 1. arrives the physical and chemical performance of the SIPE of embodiment 5 according to embodiment 1.
| Serial number | Project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 1 | SIPE content | Weight % | 40.1 | 40.2 | 40.1 | 40.6 |
| 2 | Ester exchange rate | Weight % | 84.1 | 84.2 | 84.5 | 84.9 |
| 3 | Saponification number | mgKOH/g | 124.6 | 124.8 | 124.8 | 125.3 |
| 4 | Acid value | mgKOH/g | 0.39 | 0.38 | 0.36 | 0.20 |
| 5 | Transmitance | % | 95.0 | 95.2 | 95.0 | 95.3 |
| 6 | Form and aspect | APHA | 20 | 20 | 19 | 18 |
| 7 | Ash content | Weight % | 7.97 | 7.87 | 7.92 | 7.89 |
| 8 | Moisture | Weight % | 0.19 | 0.18 | 0.19 | 0.16 |
| 9 | DEG content | Weight % | 0.10 | 0.09 | 0.08 | 0.06 |
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and modifies within all scope of the present application.
Claims (9)
1. a kind of method for synthesizing M-phthalic acid binaryglycol ester -5- sodium sulfonate, the method includes there are catalyst groups
In the case where closing object, and under the reaction temperature less than or equal to 185 DEG C, make Sodium Dimethyl Isophthalate-5-sulfonate and second
Glycol reacts under an inert atmosphere；Wherein the carbon monoxide-olefin polymeric includes at least one alkali metal acylate and at least one
Alkaline-earth metal acylate.
2. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as described in claim 1, which is characterized in that institute
Stating alkali metal acylate includes sodium acetate, and the alkaline-earth metal acylate includes calcium acetate.
3. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as claimed in claim 2, which is characterized in that institute
Stating carbon monoxide-olefin polymeric further includes nickel acetate.
4. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as claimed in claim 2, which is characterized in that with
It is counted on the basis of quality, the dosage of sodium acetate is the 0.05%-0.1% of Sodium Dimethyl Isophthalate-5-sulfonate dosage.
5. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as claimed in claim 2, which is characterized in that with
It is counted on the basis of quality, the dosage of calcium acetate is the 0.15%-0.3% of Sodium Dimethyl Isophthalate-5-sulfonate dosage.
6. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as claimed in claim 3, which is characterized in that with
It is counted on the basis of quality, the dosage of nickel acetate is the 0.02%-0.12% of Sodium Dimethyl Isophthalate-5-sulfonate dosage.
7. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as claimed in claim 3, which is characterized in that with
It is counted on the basis of molal quantity, ethylene glycol is greater than 2:1 relative to the usage ratio of Sodium Dimethyl Isophthalate-5-sulfonate.
8. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as described in claim 1, which is characterized in that institute
Stating reaction temperature is 130 DEG C -185 DEG C.
9. the method for synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate as claimed in claim 3, which is characterized in that
When adding catalyst into reaction mass, the sodium acetate of whole calcium acetate and first part is first added, is made a reservation for wait react
After period, then add the sodium acetate and nickel acetate of remainder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811381327.2A CN109320440A (en) | 2018-11-20 | 2018-11-20 | A method of synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate |
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| CN201811381327.2A CN109320440A (en) | 2018-11-20 | 2018-11-20 | A method of synthesis M-phthalic acid binaryglycol ester -5- sodium sulfonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057612A (en) * | 2021-12-27 | 2022-02-18 | 江苏恒科新材料有限公司 | Method for preparing diethylene glycol isophthalate-5-sodium sulfonate by using isophthalic acid-5-sodium sulfonate direct esterification method |
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| CN107557902A (en) * | 2017-09-07 | 2018-01-09 | 江苏恒科新材料有限公司 | A kind of preparation method of cation dyeable polyester POY silks |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114057612A (en) * | 2021-12-27 | 2022-02-18 | 江苏恒科新材料有限公司 | Method for preparing diethylene glycol isophthalate-5-sodium sulfonate by using isophthalic acid-5-sodium sulfonate direct esterification method |
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Application publication date: 20190212 |