CN105693519A - Preparation method of low-melting-point mixture of diesters of terephthalic acid - Google Patents
Preparation method of low-melting-point mixture of diesters of terephthalic acid Download PDFInfo
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- CN105693519A CN105693519A CN201410705596.5A CN201410705596A CN105693519A CN 105693519 A CN105693519 A CN 105693519A CN 201410705596 A CN201410705596 A CN 201410705596A CN 105693519 A CN105693519 A CN 105693519A
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Abstract
The invention relates to a preparation method of terephthalate n-butyl.isobutyl ester and a preparation method of low-melting-point mixture of diesters of terephthalic acid. According to the preparation method, dimethyl terephthalate and mixed liquor of n-butanol and isobutanol are used as raw materials, and high-temperature-resistant acidic resin is used as a catalyst. The disadvantage that a product is hard to separate, separation processes are many, and there are lots of waste liquids in the prior art is overcome. Instruments and equipment used in the process by the method are simple. In addition, operation steps are simple, and yield of the target product is high.
Description
Technical field
The present invention relates to the mixture of the bis-terephthalate with low melting point, further relate to the preparation method of a kind of p-phthalic acid positive fourth isobutyl ester and the preparation method of a kind of di-n-butyl terephthalate and isobutyl terephthalate low-melting mixtures。
Background technology
Bis-terephthalate, such as di-n-butyl terephthalate (DBT), isobutyl terephthalate (DIBT), can be used for producing the multiple polymeric materials such as polrvinyl chloride as plasticizer。Di-n-butyl terephthalate fusing point about 16 DEG C, isobutyl terephthalate fusing point about 54 DEG C, its dystectic character will cause that these products easily solidify at lower temperature, when using these products, heating tank, feed-line and relevant process equipment need to be installed thus causing, therefore increasing investment operating cost。The present invention solves the problems referred to above by preparing the bis-terephthalate with reduction fusing point。
In current patent, the preparation method that only patent CN101657410A describes low melting point bis-terephthalate's mixture in detail。This method uses the metallo-organic compound that can be dissolved in alcohol and bis-terephthalate's mixture as ester exchange catalyst, such as tetraisopropoxy titanium, tin tetraethoxide, zirconium tetraisopropoxide etc.。These metal organic ester exchange catalysts meet water can decompose inactivation, and therefore reagent must be strictly anhydrous, and instrument and equipment must keep dry。It addition, reaction terminates, these metallo-organic compounds being removed, just handy dilute NaOH solution processes, thus adds washing and reduced vacuum and the multiple working procedure such as dry。Top it all off, thus bring a large amount of waste water, the great harm to environment structure。
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, the preparation method of a kind of p-phthalic acid positive fourth isobutyl ester and the preparation method of the low-melting mixtures of a kind of bis-terephthalate are provided, described method uses high temperature resistant acidic resin as ester exchange catalyst, overcomes in existing patented technology product compared with difficult separation, the shortcoming such as separation circuit is many, waste liquid is many。Furthermore, the present invention is less harsh to reagent requirement, and the instrument and equipment used is simple, and simple operating steps。The more important thing is, target product yield is high。
The present invention is achieved by the following technical solutions:
The preparation method of the positive fourth isobutyl ester of a kind of p-phthalic acid, for using acidic resins as ester exchange catalyst, with dimethyl terephthalate (DMT), n-butyl alcohol and isobutanol for raw material, ester exchange reaction prepares the positive fourth isobutyl ester of p-phthalic acid。
Reaction can be represented by formulas below:
The preparation method of the positive fourth isobutyl ester of described a kind of p-phthalic acid, specifically includes following steps:
(1) under stirring condition, the n-butyl alcohol of dimethyl terephthalate (DMT) and certain proportioning and the mixed liquor of isobutanol is added in reaction distillation device, then heat up, after dimethyl terephthalate (DMT) is completely dissolved, add acid resin catalyst, carrying out ester exchange reaction and generate the positive fourth isobutyl ester of p-phthalic acid, the temperature controlling reaction makes the methanol condensed of generation ooze；
(2) add at set intervals and the mixed liquor of equal amount in step (1), the n-butyl alcohol of identical proportioning and isobutanol, until ester exchange reaction is complete；
(3) after reaction terminates, Filtration of catalyst obtains crude product, is slowly heated up by crude product, and decompression is distilled off remaining alcohol and ethers until dripless oozes, it is thus achieved that the positive fourth isobutyl ester of product p-phthalic acid；
Wherein,
Preferably, in step (1), the mixed liquor of described n-butyl alcohol and isobutanol and the mol ratio of dimethyl terephthalate (DMT) are 2～10:1, more preferably 4～8:1。
Preferably, in step (1), described n-butyl alcohol and in isobutanol mixed liquor, n-butyl alcohol and isobutanol mol ratio are 1/6～6:1, more preferably 1/4～4:1。
Preferably, the consumption of described acid resin catalyst accounts for the 15%～40% of described dimethyl terephthalate (DMT) gross weight, more preferably 25～35%。
Preferably, described acidic resins are resistant to elevated temperatures highly acidic resin, more preferably Amberlyst70 (the highest tolerable temperature is 190 DEG C), Amberlyst35 (the highest tolerable temperature is 150 DEG C), Amberlyst36 (the highest tolerable temperature is 150 DEG C), poly-benzophenone sulfonate resin (SPF, its operation temperature is high, Heat stability is good), Nafion resin (the highest tolerable temperature is 180～190 DEG C), metal-modified sulfonate resin (the domestic sulfonate resin doping Pd such as former 742, the sky former 7120 in D001 as former in sky, sky2+、Ce3+、Al3+、Fe3+、Zn2+、Cu2+、Ni2+Deng the modified resin that metal cation obtains, before these domestic sulfonate resins are modified, the highest tolerable temperature is generally 120 DEG C, can tolerate higher temperature after doping vario-property)。
Preferably, described transesterification reaction temperature is 120～160 DEG C, more preferably 127～155 DEG C。
Preferably, by reload temperature meter in described reaction distillation device, for detecting the vapor (steam) temperature distilled out, such that it is able to adjust heating-up temperature accordingly, so that reaction is in optimum temperature。
Preferably, in step (2), at interval of 4～10h add described with equal amount in step (1), the mixed liquor of the n-butyl alcohol of identical proportioning and isobutanol, more preferably 6～8h；It is more preferably 7 hours。
Preferably, add 1～3 time, more preferably add 2 times。
Preferably, ester exchange reaction total time described in step (1) and step (2) is 12～30h, more preferably 15～24h。
Preferably, the total amount of mixed liquor of step (1) and the middle n-butyl alcohol added of step (2) and isobutanol is 10～30:1 with the mol ratio of dimethyl terephthalate (DMT), more preferably 18～24:1。
Preferably, in step (3), the vacuum of described decompression distillation is 0.04～0.1MPa, more preferably 0.08MPa～0.1MPa；Decompression distillation final temperature is 115～142 DEG C, more preferably 125～135 DEG C。
During decompression distillation, temperature is slowly gone up, firm starting temperature adjust relatively low just have alcohols and by-product ethers etc. condensation ooze, in order to alcohols and by-product ethers are thoroughly eliminated, so vacuum distillation temperature slowly to be heightened, namely lower temperature no liquid oozes and just temperature is raised a bit, continues distillation, but premise is that two ester admixtures namely product not being included the positive fourth isobutyl ester of p-phthalic acid are to being steamed out。In a word, vacuum distillation temperature is too low, and unreacted alcohols and by-product ethers are not divisible；If vacuum distillation temperature is too high, then it is likely to result in dibutyl ester product and is carried over losing。
The above-mentioned positive fourth isobutyl ester of prepared product p-phthalic acid is likely to comprise di-n-butyl terephthalate and isobutyl terephthalate。
The preparation method that the present invention furthermore provides the low-melting mixtures of a kind of bis-terephthalate, for using acidic resins as catalyst for ester exchange reaction, with dimethyl terephthalate (DMT) and alcohol two kinds different for raw material, ester exchange reaction prepares the mixture of bis-terephthalate。
Preferably, the preparation method of the low-melting mixtures of a kind of bis-terephthalate, specifically include following steps:
(1) under stirring condition, the mixed liquor of two kinds of different alcohol of dimethyl terephthalate (DMT) and certain proportioning is added in reaction distillation device, then heat up, after dimethyl terephthalate (DMT) is completely dissolved, add acid resin catalyst, carrying out ester exchange reaction and generate the mixture of bis-terephthalate, the temperature controlling reaction makes the methanol condensed of generation ooze；
(2) add at set intervals and the mixed liquor of two kinds of different alcohol of equal amount, identical proportioning in step (1), until ester exchange reaction is complete；
(3) after reaction terminates, Filtration of catalyst obtains crude product, is slowly heated up by crude product, and decompression is distilled off remaining alcohol and ethers until dripless oozes, it is thus achieved that the low-melting mixtures of described bis-terephthalate；
Wherein,
Preferably, the mixed liquor of the alcohol that the two is different is the mixed liquor of n-butyl alcohol and isobutanol。
Preferably, described n-butyl alcohol and in isobutanol mixed liquor, n-butyl alcohol and isobutanol mol ratio are 1/6～6, more preferably 1/4～4。
Preferably, in step (1), the mol ratio of described n-butyl alcohol and isobutanol mixed liquor and dimethyl terephthalate (DMT) is 2～10, more preferably 4～8。
Preferably, the consumption of described acid resin catalyst accounts for the 15%～40% of described dimethyl terephthalate (DMT) gross weight, more preferably 25～35%。
Preferably, described acidic resins are resistant to elevated temperatures highly acidic resin, more preferably Amberlyst70 (the highest tolerable temperature is 190 DEG C), Amberlyst35 (the highest tolerable temperature is 150 DEG C), Amberlyst36 (the highest tolerable temperature is 150 DEG C), poly-benzophenone sulfonate resin (SPF, its operation temperature is high, Heat stability is good), Nafion resin (the highest tolerable temperature is 180～190 DEG C), metal-modified sulfonate resin (the domestic sulfonate resin doping Pd such as former 742, the sky former 7120 in D001 as former in sky, sky2+、Ce3+、Al3+、Fe3+、Zn2+、Cu2+、Ni2+Deng the modified resin that metal cation obtains, before these domestic sulfonate resins are modified, the highest tolerable temperature is generally 120 DEG C, can tolerate higher temperature after doping vario-property)。
Preferably, in step (1), described transesterification reaction temperature is 120～160 DEG C, more preferably 127～155 DEG C。
Preferably, by reload temperature meter in described reaction distillation device, for detecting the vapor (steam) temperature distilled out, such that it is able to adjust heating-up temperature accordingly, so that reaction is in optimum temperature。
Preferably, in step (2), add the mixed liquor of two kinds of different alcohol of described equal amount, identical proportioning, more preferably 6～8h at interval of 4～10h, more preferably 7 hours。
Preferably, the number of times added is 1～3, more preferably adds 2 times。
Preferably, step (1) and the middle n-butyl alcohol added of step (2) and the total amount of isobutanol mixed liquor are 10～30 with the mol ratio of dimethyl terephthalate (DMT), more preferably 18～24。
Preferably, ester exchange reaction total time described in step (1) and step (2) is 12～30h, more preferably 15～24h。
Preferably, in step (3), the vacuum that the vacuum of described decompression distillation is described decompression distillation is 0.04-0.1MPa, more preferably 0.08MPa～0.1MPa；Decompression distillation final temperature is 115～142 DEG C, more preferably 125～135 DEG C。
The low-melting mixtures of above-mentioned prepared bis-terephthalate at least includes two kinds in the positive fourth isobutyl ester of p-phthalic acid, di-n-butyl terephthalate and isobutyl terephthalate。
The present invention controls the limit of reaction by the mode of reaction distillation, the methanol generated is removed in time in reaction system；The present invention uses high temperature resistant acidic resin as catalyst, overcomes in existing patented technology product compared with difficult separation, the shortcoming such as separation circuit is many, waste liquid is many。Furthermore, the present invention is less harsh to reagent requirement, and the instrument and equipment used is simple, and simple operating steps。The more important thing is, target product yield is high。
Detailed description of the invention
Below by way of specific instantiation, technical scheme is described。Should be understood that one or more method steps that the present invention mentions do not repel before and after described combination step, there is also additive method step or additive method step can also be inserted between these steps specifically mentioned；Should also be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention。And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not for limiting the ordering of various method steps or limiting the enforceable scope of the present invention, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention。
Embodiment 1 is prepared the positive fourth isobutyl ester of p-phthalic acid by the n-butyl alcohol of 1:1 and the mixed liquor of isobutanol
To equipped with the there-necked flask of stirring paddle adds 0.3mol dimethyl terephthalate (DMT) (DMT), 1mol n-butyl alcohol, 1mol isobutanol, it is warming up to 120 DEG C, after DMT is completely dissolved, add 17.46gAmberlyst70 resin, control reaction temperature between 140～155 DEG C, allow drop ooze speed controlling at 3～6 per second, add 1mol n-butyl alcohol, 1mol isobutanol every 7h, add altogether secondary, terminate after reaction 21h。
After ester exchange reaction completes, filter hard resin, then reacting coarse product is joined in the flask of cleaning, and after adding a little crackle ware sheet, carry out decompression distillation, vacuum degree control, at 0.08MPa, slowly raises vapo(u)rizing temperature and oozes to no liquid, and vapo(u)rizing temperature is less than 142 DEG C。Finished product after decompression distillation is through capillary gas chromatography, and composition is listed in the table below 1。The finished product weight 75.985g separated, the theoretical amount of product is 83.50g, and therefore total recovery is 91.0%。
Embodiment 2
Repeat reaction described in embodiment 1, be raw material by the n-butyl alcohol that mol ratio is 3:1 and isobutanol mixed liquor accordingly。
To equipped with the there-necked flask of stirring paddle adds 0.3mol dimethyl terephthalate (DMT) (DMT), 1.5mol n-butyl alcohol, 0.5mol isobutanol, it is warming up to 120 DEG C, after DMT is completely dissolved, add 17.46gAmberlyst70 resin, control reaction temperature between 140～155 DEG C, allow drop ooze speed controlling at 3～6 per second, add 1.5mol n-butyl alcohol, 0.5mol isobutanol every 7h, add altogether secondary, terminate after reaction 21h。
After ester exchange reaction completes, filter hard resin, then reacting coarse product is joined in the flask of cleaning, and after adding a little crackle ware sheet, carry out decompression distillation, vacuum degree control, at 0.08MPa, slowly raises vapo(u)rizing temperature and oozes to no liquid, and vapo(u)rizing temperature is less than 142 DEG C。Finished product after decompression distillation is through capillary gas chromatography, and composition is listed in the table below 1。The finished product weight 76.570g separated, the theoretical amount of product is 83.50g, and therefore total recovery is 91.7%。
Embodiment 3
Repeat reaction described in embodiment 1, be raw material by the n-butyl alcohol that mol ratio is 1:3 and isobutanol mixed liquor accordingly。
To equipped with the there-necked flask of stirring paddle adds 0.3mol dimethyl terephthalate (DMT) (DMT), 0.5mol n-butyl alcohol, 1.5mol isobutanol, it is warming up to 120 DEG C, after DMT is completely dissolved, add 17.46gAmberlyst35 resin, control reaction temperature between 125～140 DEG C, allow drop ooze speed controlling at 3～6 per second, add 0.5mol n-butyl alcohol, 1.5mol isobutanol every 7h, add altogether secondary, terminate after reaction 21h。
After ester exchange reaction completes, filter hard resin, then reacting coarse product is joined in the flask of cleaning, and after adding a little crackle ware sheet, carry out decompression distillation, vacuum degree control, at 0.08MPa, slowly raises vapo(u)rizing temperature and oozes to no liquid, and vapo(u)rizing temperature is less than 142 DEG C。Finished product after decompression distillation is through capillary gas chromatography, and composition is listed in the table below 1。The finished product weight 76.987g separated, the theoretical amount of product is 83.50g, and therefore total recovery is 92.2%。
Embodiment 4
To equipped with the there-necked flask of stirring paddle adds 0.3mol dimethyl terephthalate (DMT) (DMT), 0.5mol n-butyl alcohol, 0.5mol isobutanol, it is warming up to 120 DEG C, after DMT is completely dissolved, add 23.28gAmberlyst36 resin, then control reaction temperature between 140～155 DEG C, allow drop ooze speed controlling at 3～6 per second, add 0.5mol n-butyl alcohol, 0.5mol isobutanol every 7h, add altogether secondary, terminate after reaction 21h。
After ester exchange reaction completes, filter hard resin, then reacting coarse product is joined in the flask of cleaning, and after adding a little crackle ware sheet, carry out decompression distillation, vacuum degree control, at 0.08MPa, slowly raises vapo(u)rizing temperature and oozes to no liquid, and vapo(u)rizing temperature is less than 142 DEG C。Finished product after decompression distillation is through capillary gas chromatography, and composition is listed in the table below 1。The finished product weight 75.484g separated, the theoretical amount of product is 83.50g, and therefore total recovery is 90.4%。
Embodiment 5
To equipped with the there-necked flask of stirring paddle adds 0.3mol dimethyl terephthalate (DMT) (DMT), 2.5mol n-butyl alcohol, 0.5mol isobutanol, it is warming up to 120 DEG C, after DMT is completely dissolved, add 8.75gAmberlyst70 resin, rear control reaction temperature, between 140～155 DEG C, allows drop ooze speed controlling at 3～6 per second, adds 2.5mol n-butyl alcohol, 0.5mol isobutanol every 7h, add altogether secondary, terminate after reaction 21h。
After ester exchange reaction completes, filter hard resin, then reacting coarse product is joined in the flask of cleaning, and after adding a little crackle ware sheet, carry out decompression distillation, vacuum degree control, at 0.08MPa, slowly raises vapo(u)rizing temperature and oozes to no liquid, and vapo(u)rizing temperature is less than 142 DEG C。Finished product after decompression distillation is through capillary gas chromatography, and composition is listed in the table below 1。The finished product weight 76.236g separated, the theoretical amount of product is 83.50g, and therefore total recovery is 91.3%。
Comparative example 1
Repeat reaction described in embodiment 1, be raw material by pure butanol accordingly。
To equipped with the there-necked flask of stirring paddle adds 0.3mol dimethyl terephthalate (DMT) (DMT), 2mol n-butyl alcohol, it is warming up to 120 DEG C, after DMT is completely dissolved, add 17.46gAmberlyst70, rear control reaction temperature, between 145～155 DEG C, allows drop ooze speed controlling at 3～6 per second, adds 2mol n-butyl alcohol every 7h, add altogether secondary, terminate after reaction 21h。
After ester exchange reaction completes, filter hard resin, then reacting coarse product is joined in the flask of cleaning, and after adding a little crackle ware sheet, carry out decompression distillation, vacuum degree control, at about 0.08MPa, slowly raises vapo(u)rizing temperature and oozes to no liquid, and vapo(u)rizing temperature is less than 142 DEG C。Finished product after decompression distillation is through capillary gas chromatography, and composition is listed in the table below 1。The finished product weight 77.238g separated, the theoretical amount of product is 83.50g, and therefore total recovery is 92.5%。
Comparative example 2
Repeat reaction described in embodiment 1, obtained product by pure isobutanol accordingly。
To equipped with the there-necked flask of stirring paddle adds 0.3mol dimethyl terephthalate (DMT) (DMT), 2mol isobutanol, it is warming up to 120 DEG C, after DMT is completely dissolved, add 17.46gNafion resin, rear control reaction temperature, between 127～137 DEG C, allows drop ooze speed controlling at 3～6 per second, adds 2mol isobutanol every 7h, add altogether secondary, terminate after reaction 21h。
After ester exchange reaction completes, filter hard resin, then reacting coarse product is joined in the flask of cleaning, and after adding a little crackle ware sheet, carry out decompression distillation, vacuum degree control, at about 0.08MPa, slowly raises vapo(u)rizing temperature and oozes to no liquid, and vapo(u)rizing temperature is less than 142 DEG C。Finished product after decompression distillation is through capillary gas chromatography, and composition is listed in the table below 1。The finished product weight 77.739g separated, the theoretical amount of product is 83.50g, and therefore total recovery is 93.1%。
Table 1:
Freezing point is studied
The instrument that can do the research of DSC point owing to touching cannot test relatively low temperature, and we have to simply measure the freezing point of above-mentioned ester interchange intermixture product with cryogenic thermometer by the liquid nitrogen type of cooling, and measurement result is listed in the table below 2。
Table 2:
| Blend sample | Freezing point/DEG C |
| Embodiment 1 | -28 |
| Embodiment 2 | -24 |
| Embodiment 3 | 8 |
| Embodiment 4 | 9 |
| Embodiment 5 | 6 |
| Comparative example 1 | 15.8 |
| Comparative example 2 | 46 |
By table 2 it was found that carry out ester exchange reaction with mixed alcohol can obtain subzero dibutyl terephthalate mixture, in embodiment, minimum freezing point is up to-28 DEG C, and the n-butyl alcohol of its correspondence and isobutanol mol ratio are 1:1。Associative list 1, we analyze draw the freezing point of dibutyl terephthalate mixture and its form between substantially have such relation: the freezing point of dibutyl terephthalate mixture is determined by the total content of the positive fourth isobutyl ester of p-phthalic acid with di-n-butyl terephthalate (DBT), both total contents are more high, then the freezing point of mixture is more low；When both total contents are more or less the same, the freezing point of mixture is played conclusive effect by the content of p-phthalic acid positive fourth isobutyl ester, and namely the content of p-phthalic acid positive fourth isobutyl ester is more high, and the freezing point of mixture is more low。
Claims (15)
1. a preparation method for the positive fourth isobutyl ester of p-phthalic acid, for using acidic resins as ester exchange catalyst, with dimethyl terephthalate (DMT), n-butyl alcohol and isobutanol for raw material, ester exchange reaction prepares the positive fourth isobutyl ester of p-phthalic acid。
2. the preparation method of the positive fourth isobutyl ester of a kind of p-phthalic acid as claimed in claim 1, it is characterised in that specifically include following steps:
(1) under stirring condition, the n-butyl alcohol of dimethyl terephthalate (DMT) and certain proportioning and the mixed liquor of isobutanol is added in reaction distillation device, then heat up, after dimethyl terephthalate (DMT) is completely dissolved, add acid resin catalyst, carrying out ester exchange reaction and generate the positive fourth isobutyl ester of p-phthalic acid, the temperature controlling reaction makes the methanol condensed of generation ooze；
(2) add at set intervals and the mixed liquor of equal amount in step (1), the n-butyl alcohol of identical proportioning and isobutanol, until ester exchange reaction is complete；
(3) after reaction terminates, Filtration of catalyst obtains crude product, is slowly heated up by crude product, and decompression is distilled off remaining alcohol and ethers until dripless oozes, it is thus achieved that the positive fourth isobutyl ester of product p-phthalic acid。
3. the preparation method of the positive fourth isobutyl ester of a kind of p-phthalic acid as claimed in claim 1 or 2, it is characterised in that described acidic resins are resistant to elevated temperatures highly acidic resin。
4. the preparation method of the positive fourth isobutyl ester of a kind of p-phthalic acid as claimed in claim 3, it is characterized in that, acidic resins are selected from Amberlyst70, Amberlyst35, Amberlyst36, poly-benzophenone sulfonate resin, Nafion resin and metal-modified sulfonate resin。
5. the preparation method of the positive fourth isobutyl ester of a kind of p-phthalic acid as claimed in claim 2, it is characterised in that the consumption of described acid resin catalyst accounts for the 15%～40% of described dimethyl terephthalate (DMT) gross weight。
6. the preparation method of the positive fourth isobutyl ester of a kind of p-phthalic acid as claimed in claim 2, it is characterised in that step (1) also includes any one of following characteristics or multinomial:
A the mixed liquor of () described n-butyl alcohol and isobutanol and the mol ratio of dimethyl terephthalate (DMT) are 2～10:1；
B, in () described n-butyl alcohol and isobutanol mixed liquor, n-butyl alcohol and isobutanol mol ratio are 1/6～6:1。
7. the preparation method of the positive fourth isobutyl ester of a kind of p-phthalic acid as claimed in claim 2, it is characterised in that also include any one in following characteristics or multinomial:
A () described transesterification reaction temperature is 120～160 DEG C；
In (b) step (2), at interval of 4～10h add described with equal amount in step (1), the mixed liquor of the n-butyl alcohol of identical proportioning and isobutanol；Add 1～3 time；
C the n-butyl alcohol added in () step (1) and step (2) and the total amount of mixed liquor of isobutanol are 10～30:1 with the mol ratio of dimethyl terephthalate (DMT)；
D ester exchange reaction total time described in () step (1) and step (2) is 12～30h；
In (e) step (3), the vacuum 0.04～0.1MPa of described decompression distillation；Decompression distillation final temperature is 115～142 DEG C。
8. the preparation method of the low-melting mixtures of a bis-terephthalate, it is characterized in that, for using acidic resins as catalyst for ester exchange reaction, with dimethyl terephthalate (DMT) and alcohol two kinds different for raw material, ester exchange reaction prepares the mixture of bis-terephthalate。
9. the preparation method of the low-melting mixtures of a kind of bis-terephthalate as claimed in claim 8, it is characterised in that specifically include following steps:
(1) under stirring condition, the mixed liquor of two kinds of different alcohol of dimethyl terephthalate (DMT) and certain proportioning is added in reaction distillation device, then heat up, after dimethyl terephthalate (DMT) is completely dissolved, add acid resin catalyst, carrying out ester exchange reaction and generate the mixture of bis-terephthalate, the temperature controlling reaction makes the methanol condensed of generation ooze；
(2) add at set intervals and the mixed liquor of two kinds of different alcohol of equal amount, identical proportioning in step (1), until ester exchange reaction is complete；
(3) after reaction terminates, Filtration of catalyst obtains crude product, is slowly heated up by crude product, and decompression is distilled off remaining alcohol and ethers until dripless oozes, it is thus achieved that the low-melting mixtures of described bis-terephthalate。
10. the preparation method of the low-melting mixtures of a kind of bis-terephthalate as claimed in claim 8 or 9, it is characterised in that described acidic resins are resistant to elevated temperatures highly acidic resin。
11. the preparation method of the low-melting mixtures of a kind of bis-terephthalate as claimed in claim 10, it is characterized in that, described acidic resins are selected from Amberlyst70, Amberlyst35, Amberlyst36, poly-benzophenone sulfonate resin, Nafion resin and metal-modified sulfonate resin。
12. the preparation method of the low-melting mixtures of a kind of bis-terephthalate as claimed in claim 9, it is characterised in that the consumption of described acid resin catalyst accounts for the 15%～40% of described dimethyl terephthalate (DMT) gross weight。
13. the preparation method of the low-melting mixtures of a kind of bis-terephthalate as claimed in claim 8 or 9, it is characterised in that the mixed liquor of the alcohol that the two is different is the mixed liquor of n-butyl alcohol and isobutanol。
14. the preparation method of the low-melting mixtures of a kind of bis-terephthalate as claimed in claim 13, it is characterised in that also include any one in following characteristics or multinomial:
A, in () described n-butyl alcohol and isobutanol mixed liquor, n-butyl alcohol and isobutanol mol ratio are 1/6～6:1；
B the mixed liquor of () described n-butyl alcohol and isobutanol and the mol ratio of dimethyl terephthalate (DMT) are 2～10:1。
15. the preparation method of the low-melting mixtures of a kind of bis-terephthalate as claimed in claim 9, it is characterised in that also include any one in following characteristics or multinomial:
A () described transesterification reaction temperature is 120～160 DEG C；
In (b) step (2), add the mixed liquor of two kinds of different alcohol of described equal amount, identical proportioning at interval of 4～10h；Add 1～3 time；
C the n-butyl alcohol added in () step (1) and step (2) and the total amount of mixed liquor of isobutanol are 10～30:1 with the mol ratio of dimethyl terephthalate (DMT)；
D ester exchange reaction total time described in () step (1) and step (2) is 12～30h；
In (e) step (3), the vacuum 0.04～0.1MPa of described decompression distillation；Decompression distillation final temperature is 115～142 DEG C。
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| CN201410705596.5A Pending CN105693519A (en) | 2014-11-27 | 2014-11-27 | Preparation method of low-melting-point mixture of diesters of terephthalic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053440A (en) * | 2018-08-20 | 2018-12-21 | 苏州市湘园特种精细化工有限公司 | A kind of preparation method of dioctadecyl terephthalate |
| CN115433087A (en) * | 2022-09-07 | 2022-12-06 | 福建农林大学 | Method for extracting dibutyl terephthalate from Raffaelea lauricola |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219950A (en) * | 2008-01-25 | 2008-07-16 | 天津大学 | System and method for producing n-butyl acetate by using methyl acetate and n-butyl alcohol ester exchange reaction |
| CN101535233A (en) * | 2006-11-20 | 2009-09-16 | 赢创德固赛有限责任公司 | Process for preparing alkyl esters of fatty acids and acrolein from triglycerides |
| CN101657410A (en) * | 2007-04-18 | 2010-02-24 | 伊士曼化工公司 | Low-melting mixtures of di-n-butyl and diisobutyl terephthalate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101535233A (en) * | 2006-11-20 | 2009-09-16 | 赢创德固赛有限责任公司 | Process for preparing alkyl esters of fatty acids and acrolein from triglycerides |
| CN101657410A (en) * | 2007-04-18 | 2010-02-24 | 伊士曼化工公司 | Low-melting mixtures of di-n-butyl and diisobutyl terephthalate |
| CN101219950A (en) * | 2008-01-25 | 2008-07-16 | 天津大学 | System and method for producing n-butyl acetate by using methyl acetate and n-butyl alcohol ester exchange reaction |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053440A (en) * | 2018-08-20 | 2018-12-21 | 苏州市湘园特种精细化工有限公司 | A kind of preparation method of dioctadecyl terephthalate |
| CN115433087A (en) * | 2022-09-07 | 2022-12-06 | 福建农林大学 | Method for extracting dibutyl terephthalate from Raffaelea lauricola |
| CN115433087B (en) * | 2022-09-07 | 2023-09-12 | 福建农林大学 | Method for extracting dibutyl terephthalate from Raffaelea lauricola |
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