CN108147372B - Preparation method of sodium sulfide reaction precursor in polyphenylene sulfide production - Google Patents
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Abstract
The invention relates to a production method of polyphenylene sulfide, and particularly discloses a preparation method of a sodium sulfide reaction precursor in polyphenylene sulfide productionThe method comprises the following steps: A. dissolving: adding raw materials into a pre-reaction kettle according to a certain proportion, wherein the raw materials comprise sodium sulfide dihydrate and an entrainer, and the entrainer is an amide compound; adding water into the system to ensure Na in the system2S and H2The molar ratio of O is 1: 10-20, then oxygen in the pre-reaction kettle is removed, and then the mixture is heated to 150-180 ℃ and maintained at the temperature for at least 30min to obtain an intermediate; B. and (3) dehydrating: and distilling to remove excessive water in the intermediate to obtain a sodium sulfide reaction precursor. The invention has the advantages that: 1) the preparation time of the sodium sulfide reaction precursor can be shortened from 4-6 h to 2-3 h, the process energy consumption is correspondingly reduced by more than 50%, and the preparation method has remarkable economic and environment-friendly values; 2) the scheme is simple to implement and is beneficial to industrial popularization.
Description
Technical Field
The invention relates to a synthesis process of high polymer material resin, in particular to a synthesis process of polyphenylene sulfide.
Background
The polyphenylene sulfide synthesis route mainly comprises three routes, namely a sodium sulfide method, a sulfur solution method and an oxidative polymerization method, and the most adopted technology for industrial synthesis is the sodium sulfide method.
The prior process for synthesizing polyphenylene sulfide by a sodium sulfide method is to take p-dichlorobenzene and sodium sulfide as raw materials to carry out dehydration, polycondensation and other process steps to prepare the polyphenylene sulfide. The method mainly comprises the following steps:
(1) dehydrating the hydrous sodium sulfide to obtain a sodium sulfide reaction precursor;
(2) in a polymerization kettle, the sodium sulfide reaction precursor and p-dichlorobenzene (p-DCB) are subjected to polymerization reaction to obtain the polyphenylene sulfide product.
Because sodium sulfide has strong water absorption and is difficult to store, anhydrous sodium sulfide is expensive and has high cost, sodium sulfide containing crystal water, namely sodium sulfide dihydrate, is generally used in the synthesis process of polyphenylene sulfide, and the sodium sulfide dihydrate needs to be dehydrated before the polyphenylene sulfide is synthesized (because the sodium sulfide containing crystal water affects the condensation polymerization reaction process of sodium sulfide and p-dichlorobenzene in the production process of polyphenylene sulfide). The mainstream dehydration method at present is to mix sodium sulfide dihydrate and entrainer and then heat and dehydrate the mixture.
For example, in the invention patent application with the publication number of CN103788373B, a dehydration process of sodium sulfide polyhydrate in the synthesis of polyphenylene sulfide resin is introduced, wherein in the dehydration stage of sodium sulfide polyhydrate as a raw material, sodium sulfide polyhydrate, a catalyst and an NMP solution are heated and stirred in a reaction kettle, the temperature is continuously increased to 150-200 ℃, and the sodium sulfide polyhydrate is dehydrated in a nitrogen gas deoxidation mode. The method is mainly characterized in that after NMP is added into a sodium sulfide system, crystallization water is removed in a heating mode in which the NMP and water form an azeotrope, but the method is high in energy consumption and high in time cost, the time of the whole dehydration process is very long, at least 4-6 hours are usually needed, and practice proves that if the dehydration time is shortened, the polycondensation reaction is not facilitated, and the quality of a polyphenylene sulfide product cannot be guaranteed.
Disclosure of Invention
The invention provides a preparation method of a sodium sulfide reaction precursor in polyphenylene sulfide production, which aims to shorten the dehydration time of sodium sulfide dihydrate and reduce the dehydration energy consumption.
The technical scheme adopted by the invention is as follows: the preparation method of the sodium sulfide reaction precursor in the production of the polyphenylene sulfide comprises the following steps:
A. dissolving: adding raw materials into a pre-reaction kettle according to a certain proportion, wherein the raw materials comprise sodium sulfide dihydrate and an entrainer, and the entrainer is an amide compound; adding water into the system to ensure Na in the system2S and H2The molar ratio of O is 1: 10-20, then oxygen in the pre-reaction kettle is removed, and then the mixture is heated to 150-180 ℃ and maintained at the temperature for at least 30min to obtain an intermediate;
B. and (3) dehydrating: and distilling to remove excessive water in the intermediate to obtain a sodium sulfide reaction precursor.
Wherein "Na in the System2S and H2H in a molar ratio of O of 1: 10-20 ″2The molar quantity of O is the crystal water and free water in the systemSum of molar amounts of water removed.
The inventors have considered that the preparation of the sodium sulfide reaction precursor is not only a process for removing crystal water. And proposes that: in the process of heating and dehydrating the sodium sulfide polyhydrate, crystal water is firstly heated and decomposed into free water and H in the free water+The intermediate is formed to enable the sulfur ions in the sodium sulfide to have stronger negative charges, so that a sodium sulfide reaction precursor obtained by dehydrating the intermediate is more easily combined with p-dichlorobenzene in a polycondensation reaction to promote the rapid progress of the polycondensation reaction.
The structure of the ternary complex is shown in figure 1:
the inventors therefore believe that the dehydration process of the sodium sulphide dihydrate can be understood in two stages, namely the intermediate formation stage and the intermediate moisture removal stage. It is believed that free water plays a key role in the formation process of the intermediate, the activity of the solvent is improved by the hydrogen bonding of water in the complex formed by the sodium sulfide and the amide compound such as NMP and the like, and a stable ternary complex is formed, and the water in the system needs to be free water when the hydrogen bonding occurs. We have not realized this in the past. In the conventional process, the formation of free water is actually caused by the thermal decomposition of crystal water in sodium sulfide monohydrate, which needs to absorb a large amount of heat to decompose and thus provide enough H for the system+This results in a shorter reaction time in which not enough intermediate is formed in the system and thus in a longer dehydration time, which we believe is actually the result of the long formation time of the intermediate, and thus shortening the dehydration time of the sodium sulfide monohydrate is actually critical in shortening the reaction timeTime of formation of the intermediate.
In the present invention, the inventors propose a way of adding water to provide free water to the system, which directly provides sufficient H to the system due to the direct addition of free water+Therefore, the need for intermediate formation can be satisfied without waiting for the decomposition of the crystal water, and the effect of shortening the time for intermediate formation can be achieved.
To achieve the goal of reducing the time for intermediate formation by this scheme, it is necessary to ensure that free water in the system can provide sufficient H+Otherwise, the stable complex can be generated after the crystalline water is decomposed, so that the subsequent polycondensation reaction is not influenced. Experiments prove that when H is in the system2O (including crystallized water and free water) and Na2The corresponding purpose can be achieved when the molar ratio of S is at least 10:1, but the sodium sulfide is decomposed at high temperature due to excessive water addition, so that the subsequent polycondensation reaction is abnormal. Experiment proves that H in the system2O (including crystallized water and free water) and Na2The molar ratio of S should be controlled within the range of 10-20: 1.
It should be noted that although the addition of water in the present scheme leads to a proper extension of the time consumed by the dehydration stage of the intermediate in step B, the contribution of water to the shortening of the time of the intermediate formation stage is more significant, and a certain amount of free water is left in the system after the dehydration stage is completed, which also saves a lot of time and energy consumption, and the traditional process requires thorough water removal, so that the time and energy consumption is large.
And (3) the dehydration amount of the intermediate system in the step (B) is verified through experiments, and when the liquid level is controlled to be 25-50%, the free water content of the system has no adverse effect on the later-stage polycondensation reaction.
In the invention, whether the system forms a stable ternary complex or not can be judged by measuring the free water content in the system, the water content of the system is less than that before the reaction because part of water generates the ternary complex, and the stable ternary complex is formed when the theoretically reduced water content is consistent with the mole number of sodium sulfide; a large number of experiments prove that the stable ternary complex can be formed after the reaction is carried out for 30min in the first stage. The adoption of the standard to control the production also has stronger operability.
In the present invention, the entrainer used is an amide compound such as formamide, acetamide, N-methylformamide, N-dimethylformamide, N-dimethylacetamide, 2-pyrrolidone, hexamethylphosphoramide, N-methylpyrrolidone, which are used as the entrainer in the present invention. Preferably, N-methylpyrrolidone is preferably used as the entrainer according to the invention.
As a further improvement of the invention, the raw materials comprise sodium sulfide dihydrate, N-methyl pyrrolidone, sodium hydroxide and sodium acetate in a molar ratio of 1: 5-10: 0.02: 0.02. In the scheme, a certain amount of sodium hydroxide and sodium acetate are added into raw materials, the purpose of adding the sodium hydroxide is to reduce the oxidation of sodium sulfide, the purpose of adding the sodium acetate is to reduce the hydrolysis of NMP under the alkaline and heating conditions, and the sodium acetate is also used as a third monomer of the later-stage polycondensation reaction.
As a further improvement of the invention, the method for removing oxygen in the pre-reaction kettle in the step A comprises the following steps: and introducing nitrogen into the pre-reaction kettle to replace the gas phase in the pre-reaction kettle. In addition, it is also conceivable to use other means, for example, a high vacuum to evacuate the air from the pre-reactor.
As a further improvement of the present invention, the dehydration method in step B specifically comprises: and raising the temperature of the pre-reaction kettle to 190-210 ℃, controlling the vacuum degree in the container to be 0.05-0.095 MPa by using a vacuum pump, and removing redundant water in the system in a distillation mode. The distillation is carried out under certain vacuum degree in the scheme, because the process of dehydration is that NMP and water form azeotrope evaporation dehydration, the purpose of vacuum is in order to reduce azeotrope boiling point, energy saving and time.
In the scheme, in the distillation dehydration process, when the liquid level of the pre-reaction kettle is reduced to 25-50% of the liquid level of the pre-reaction kettle before distillation, the heating is stopped. The inventors believe that water is necessary in the ternary complex, and that the free water remaining after formation of the ternary complex is superfluous. Because water and NMP are mutually soluble, the water is not removed completely, the water is controlled to a certain liquid level so as to ensure that the residual free water stops removing water without generating adverse effect on the polycondensation reaction, and meanwhile, the time and the energy are saved. The conventional process requires thorough removal of water, and is therefore extremely time and energy consuming. It can also be said that the formation of ternary complex by adding water saves time, and the incomplete nature of late stage water removal also saves a lot of time and energy consumption. And because water and NMP can be mutually soluble, the water content of the system is controlled in a liquid level reduction mode, and the operation is better in production. The reduction proportion of the liquid level can be adjusted within the range according to the water content of the system before dehydration.
The invention has the beneficial effects that: 1) the preparation time of the sodium sulfide reaction precursor can be shortened from 4-6 h to 2-3 h, the energy consumption of the process is correspondingly reduced by more than 50%, and the preparation method has remarkable economic and environmental protection values; 2) the scheme is simple to implement and is beneficial to industrial popularization.
Drawings
FIG. 1 is a diagram of the structure of the ternary complex formed during the dehydration of sodium sulfide dihydrate.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
adding sodium sulfide trihydrate, NMP (N-methyl pyrrolidone), sodium hydroxide and sodium acetate into a 25L pre-reaction kettle according to the molar ratio of 1:5:0.02:0.02, adding a certain amount of deionized water, controlling the adding amount of the deionized water to ensure that the molar ratio of the sodium sulfide to the water (including crystal water and free water) in the system is 1:10, opening the pre-reaction kettle before heating, simultaneously opening nitrogen to replace the gas phase space of the pre-reaction kettle for 10 minutes, then heating the system to 150 ℃ by adopting an electric heating mode, maintaining the temperature until the system completely reacts to form a stable ternary complex, and consuming 30 minutes to obtain a water-containing sodium sulfide reaction precursor (namely an intermediate).
And continuously raising the temperature of the pre-reaction kettle to 190 ℃ by using heat conduction oil, controlling the vacuum degree of a system to be 0.05MPa by using a vacuum pump, removing redundant water in the system by a distillation mode, leaving the redundant water and NMP out of the reaction system in a gas form, introducing the condensed wastewater into a solvent recovery device, and discharging the uncondensed gas after the uncondensed gas is absorbed by alkali to reach the standard. And stopping heating when the liquid level of the pre-reaction kettle is reduced to 50% of that before distillation, and taking 60min to obtain the sodium sulfide reaction precursor A.
The obtained sodium sulfide reaction precursor A is conveyed to a reaction kettle through a pipeline to carry out polycondensation reaction according to the following method, and the polyphenylene sulfide product A is prepared. The polyphenylene sulfide polycondensation process is as follows:
firstly, starting a polycondensation kettle to stir, adding metered N-methyl pyrrolidone into the polycondensation kettle before reaction, and then adding metered sodium sulfide reaction precursor A and p-dichlorobenzene solution.
And after the feeding is finished, closing the polycondensation reaction kettle and carrying out temperature rising operation according to a temperature rising curve. After the temperature rise is finished, the reaction system carries out polycondensation reaction at the reaction temperature of 260 ℃ and the pressure of 1.1MPa for 6 h.
After the reaction is finished, the polyphenylene sulfide slurry is cooled to 100 ℃ by cooling water, and then the polyphenylene sulfide slurry is placed into the slurry tank by opening the discharge valve and passing through the closed pipeline. The polyphenylene sulfide slurry is subjected to subsequent process steps of separation, washing, drying and the like to obtain a polyphenylene sulfide product A.
Example two:
adding sodium sulfide nonahydrate and formamide into a 25L pre-reaction kettle according to the molar ratio of 1:10, adding a certain amount of deionized water, controlling the adding amount of the deionized water to ensure that the molar ratio of the sodium sulfide to the water (including crystal water and free water) in the system is 1:20, opening the pre-reaction kettle for stirring before heating, simultaneously opening nitrogen to replace the gas phase space of the pre-reaction kettle for 10 minutes, then heating the system to 180 ℃ by adopting an electric heating mode, maintaining the temperature until complete reaction to form a stable ternary complex, and consuming 40 minutes to obtain a water-containing sodium sulfide reaction precursor (namely an intermediate).
And continuously heating the temperature of the pre-reaction kettle to 208 ℃ by using heat conduction oil, controlling the vacuum degree of the system to be 0.08MPa by using a vacuum pump, removing redundant water in the system in a distillation mode, enabling the redundant water and formamide to leave the reaction system in a gas form, enabling the condensed wastewater to enter a solvent recovery device, and enabling the uncondensed gas to reach the standard after being absorbed by alkali and then be discharged. And stopping heating when the liquid level of the pre-reaction kettle is reduced to 25% of that before distillation, and consuming 120min to obtain a sodium sulfide reaction precursor B.
And conveying the obtained sodium sulfide reaction precursor B to a reaction kettle through a pipeline to perform polycondensation reaction according to the method in the first embodiment to obtain a polyphenylene sulfide product B.
Example three:
adding sodium sulfide pentahydrate, 2-pyrrolidone and sodium hydroxide into a 25L pre-reaction kettle according to the molar ratio of 1:8:0.02, adding a certain amount of deionized water, controlling the adding amount of the deionized water to ensure that the molar ratio of the sodium sulfide to the water (including crystal water and free water) in the system is 1:15, opening the pre-reaction kettle for stirring before heating, simultaneously opening nitrogen to replace the gas phase space of the pre-reaction kettle for 10 minutes, then adopting an electric heating mode to raise the temperature of the system to 160 ℃, maintaining the temperature until complete reaction to form a stable ternary complex, consuming 30 minutes, and obtaining a water-containing sodium sulfide reaction precursor (namely an intermediate).
And continuously heating the temperature of the pre-reaction kettle to 200 ℃ by using heat conduction oil, controlling the vacuum degree of a system to be 0.095MPa by using a vacuum pump, removing redundant water in the system in a distillation mode, enabling the redundant water and the 2-pyrrolidone to leave the reaction system in a gas form, enabling the condensed wastewater to enter a solvent recovery device, and discharging the uncondensed gas after reaching the standard through alkali absorption. And stopping heating when the liquid level of the pre-reaction kettle is reduced to 30% of that before distillation, and taking 90min to obtain a sodium sulfide reaction precursor C.
And conveying the obtained sodium sulfide reaction precursor C to a reaction kettle through a pipeline to perform polycondensation reaction according to the method in the first embodiment to obtain the polyphenylene sulfide product C.
Comparative example four:
in a 25L pre-reaction kettle, adding sodium sulfide trihydrate, NMP (N-methyl pyrrolidone), sodium hydroxide and sodium acetate into the pre-reaction kettle according to the molar ratio of 1:5:0.02:0.02, opening the pre-reaction kettle before heating, stirring, simultaneously opening nitrogen to replace the gas phase space of the pre-reaction kettle for 10 minutes, then heating the system to 150 ℃ by adopting an electric heating mode, maintaining the temperature until complete reaction to form a stable ternary complex, and consuming 2 hours to obtain a water-containing sodium sulfide reaction precursor (namely an intermediate).
And continuously raising the temperature of the pre-reaction kettle to 190 ℃ by using heat conduction oil, controlling the vacuum degree of a system to be 0.05MPa by using a vacuum pump, removing redundant water in the system by a distillation mode, leaving the redundant water and NMP out of the reaction system in a gas form, introducing the condensed wastewater into a solvent recovery device, and discharging the uncondensed gas after the uncondensed gas is absorbed by alkali to reach the standard. And stopping heating when the liquid level of the pre-reaction kettle is reduced to 50% of that before distillation, and taking 45min to obtain the sodium sulfide reaction precursor D.
And conveying the obtained sodium sulfide reaction precursor D to a reaction kettle through a pipeline to perform polycondensation reaction according to the method in the first embodiment to obtain a polyphenylene sulfide product D.
Comparative example five:
adding sodium sulfide trihydrate, NMP (N-methyl pyrrolidone), sodium hydroxide and sodium acetate into a 25L pre-reaction kettle according to the molar ratio of 1:5:0.02:0.02, adding a certain amount of deionized water, controlling the adding amount of the deionized water to ensure that the molar ratio of the sodium sulfide to the water (including crystal water and free water) in the system is 1:5, opening the pre-reaction kettle before heating, simultaneously opening nitrogen to replace the gas phase space of the pre-reaction kettle for 10 minutes, then heating the system to 150 ℃ by adopting an electric heating mode, maintaining the temperature until the system completely reacts to form a stable ternary complex, and consuming 110 minutes to obtain a water-containing sodium sulfide reaction precursor (namely an intermediate).
And continuously raising the temperature of the pre-reaction kettle to 190 ℃ by using heat conduction oil, controlling the vacuum degree of a system to be 0.05MPa by using a vacuum pump, removing redundant water in the system by a distillation mode, leaving the redundant water and NMP out of the reaction system in a gas form, introducing the condensed wastewater into a solvent recovery device, and discharging the uncondensed gas after the uncondensed gas is absorbed by alkali to reach the standard. And stopping heating when the liquid level of the pre-reaction kettle is reduced to 50% of that before distillation, and taking 60min to obtain the sodium sulfide reaction precursor E.
And conveying the obtained sodium sulfide reaction precursor E to a reaction kettle through a pipeline to perform polycondensation reaction according to the method in the first embodiment to obtain a polyphenylene sulfide product E.
Comparative example six:
adding sodium sulfide trihydrate, NMP (N-methyl pyrrolidone), sodium hydroxide and sodium acetate into a 25L pre-reaction kettle according to the molar ratio of 1:5:0.02:0.02, opening the pre-reaction kettle for stirring before heating, simultaneously opening nitrogen to replace the gas phase space of the pre-reaction kettle for 10 minutes, then heating the system to 190 ℃ by adopting an electric heating mode, controlling the vacuum degree of the system to be 0.05MPa by utilizing a vacuum pump, then removing excessive water in the system by a distillation mode, leaving the excessive water and the NMP out of the reaction system in a gas mode, feeding condensed wastewater into a solvent recovery device, and discharging the uncondensed gas after alkali absorption to reach the standard. And (4) dehydrating for 90min, and then stopping heating to obtain a sodium sulfide reaction precursor F.
And conveying the obtained sodium sulfide reaction precursor F to a reaction kettle through a pipeline to perform polycondensation reaction according to the method in the first embodiment to obtain the polyphenylene sulfide product F.
Table 1: comparison table for time consumption of dehydration process
Table 2: polyphenylene sulfide product index detection table
Claims (6)
1. The preparation method of the sodium sulfide reaction precursor in the production of the polyphenylene sulfide comprises the following steps:
A. dissolving: adding raw materials into a pre-reaction kettle according to a certain proportionThe material comprises sodium sulfide dehydrate and an entrainer, wherein the entrainer is an amide compound; adding water into the system to ensure Na in the system2S and H2The molar ratio of O is 1: 10-20, then oxygen in the pre-reaction kettle is removed, and then the mixture is heated to 150-180 ℃ and maintained at the temperature for at least 30min to obtain an intermediate;
B. and (3) dehydrating: and distilling to remove excessive water in the intermediate to obtain a sodium sulfide reaction precursor.
2. The method for preparing the sodium sulfide reaction precursor in the production of polyphenylene sulfide as claimed in claim 1, wherein: the entrainer is selected from one of formamide, acetamide, N-methylformamide, N-dimethylformamide, N-dimethylacetamide, 2-pyrrolidone, hexamethylphosphoramide and N-methylpyrrolidone.
3. The method for preparing the sodium sulfide reaction precursor in the production of polyphenylene sulfide as claimed in claim 1, wherein: the raw materials comprise sodium sulfide dihydrate, N-methyl pyrrolidone, sodium hydroxide and sodium acetate according to the molar ratio of 1: 5-10: 0.02: 0.02.
4. The method for preparing the sodium sulfide reaction precursor in the production of polyphenylene sulfide as claimed in claim 1, wherein: the method for removing the oxygen in the pre-reaction kettle in the step A comprises the following steps: and introducing nitrogen into the pre-reaction kettle to replace the gas phase in the pre-reaction kettle.
5. The method for preparing the sodium sulfide reaction precursor in the production of polyphenylene sulfide as claimed in claim 1, wherein: the dehydration method in the step B comprises the following specific steps: and raising the temperature of the pre-reaction kettle to 190-210 ℃, controlling the vacuum degree in the container to be 0.05-0.095 MPa by using a vacuum pump, and removing redundant water in the system in a distillation mode.
6. The method for preparing the sodium sulfide reaction precursor in the production of polyphenylene sulfide as claimed in claim 5, wherein: and in the distillation dehydration process, stopping heating when the liquid level of the pre-reaction kettle is reduced to 25-50% of the liquid level of the pre-reaction kettle before distillation.
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| CN1312306A (en) * | 2000-09-30 | 2001-09-12 | 四川省华拓实业发展股份有限公司 | Polyhydrated sodium sulfide dewatering techn during production of polyphenyl thioether |
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| CN108147372A (en) | 2018-06-12 |
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