CN108147372A - The preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production - Google Patents
The preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production Download PDFInfo
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- CN108147372A CN108147372A CN201711268906.1A CN201711268906A CN108147372A CN 108147372 A CN108147372 A CN 108147372A CN 201711268906 A CN201711268906 A CN 201711268906A CN 108147372 A CN108147372 A CN 108147372A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/38—Dehydration
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
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Abstract
The present invention relates to a kind of production methods of polyphenylene sulfide, specifically disclose a kind of preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production, include the following steps：A, it dissolves：Raw material is added in pre-reactor by a certain percentage, the raw material includes wateriness sodium sulfide and entrainer, and the entrainer is amides compound；Into system plus water ensures Na in system2S and H2The molar ratio of O is 1:10~20, the oxygen in pre-reactor is then excluded, mixture is heated later and to 150~180 DEG C and maintains the temperature at least 30min, obtain intermediate；B, it is dehydrated：The excessive moisture in intermediate is sloughed in distillation, obtains vulcanized sodium reacting precursor.It is an advantage of the invention that：1) preparation time of vulcanized sodium reacting precursor can be foreshortened to 2~3h by 4~6h, and reduce more than 50% technique energy consumption accordingly, there is significant economic and environment-friendly value；2) scheme is implemented simple, conducive to industrially promoting.
Description
Technical field
The present invention relates to the synthesis technology of high molecular material resin, especially a kind of synthesis technology of polyphenylene sulfide.
Background technology
Polyphenylene sulfide synthetic route mainly has three, and sodium sulfide method, sulfur solution route, oxidative polymerization method, industry are combined to
It is sodium sulfide method using most technologies.
The technique of the polyphenylene sulfide of sodium sulfide method synthesis at present is all to be dehydrated, contracted as raw material using paracide and vulcanized sodium
It is poly- to wait processing steps and be made.Key step is as follows：
(1) aqueous vulcanized sodium is dehydrated to obtain vulcanized sodium reacting precursor；
(2) in polymeric kettle, vulcanized sodium reacting precursor occurs polymerisation with paracide (p-DCB) and obtains polyphenylene sulfide
Product.
Wherein, since the water imbibition of vulcanized sodium is strong, it is more difficult to preserve, and anhydrous sodium sulfide is expensive, and cost is very high,
Therefore the vulcanized sodium containing the crystallization water is generally used in the building-up process of polyphenylene sulfide, it that is to say wateriness sodium sulfide, therefore need
Before synthesizing polyphenylene sulfide, wateriness sodium sulfide is carried out dehydrating (this is because in the production process of polyphenylene sulfide, due to
Raw material vulcanized sodium contains the crystallization water, influences the polycondensation reaction process of vulcanized sodium and paracide).The dewatering of mainstream is at present
Thermal dehydration is carried out after wateriness sodium sulfide and entrainer are mixed.
For example, Authorization Notice No. is to describe a kind of polyphenylene sulfide in the application for a patent for invention of CN103788373B to close
It is in the raw material wateriness sodium sulfide water smoking, wateriness sodium sulfide, catalyst, NMP is molten into the dewatering process of middle wateriness sodium sulfide
Liquid is heated and is stirred in a kettle, continuous warming, and continuous warming is passed through the mode of nitrogen deoxidation to more to 150~200 DEG C
Water vulcanized sodium is dehydrated.After this method in vulcanized sodium system mainly using NMP is added in, the method for heating is used with NMP
The mode that azeotropic mixture is formed with water sloughs the crystallization water, but this method energy expenditure is big, and the time spends more, entire dewatering process flow
Time it is very long, typically at least need 4~6h, in practice it has proved that if shortening dewatering time, be unfavorable for polycondensation reaction into
Row, it is impossible to ensure the quality of polyphenylene sulfide product.
Invention content
To shorten the dewatering time of wateriness sodium sulfide, dehydration energy consumption is reduced, the present invention provides a kind of productions of polyphenylene sulfide
The preparation method of middle vulcanized sodium reacting precursor.
The technical solution adopted in the present invention is：The preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production, including
Following steps：
A, it dissolves：Raw material is added in pre-reactor by a certain percentage, the raw material includes wateriness sodium sulfide and entrainer,
The entrainer is amides compound；Into system plus water ensures Na in system2S and H2The molar ratio of O is 1:10~20, so
Heel row removes the oxygen in pre-reactor, heats mixture later and to 150~180 DEG C and maintains the temperature at least 30min, in obtaining
Mesosome；
B, it is dehydrated：The excessive moisture in intermediate is sloughed in distillation, obtains vulcanized sodium reacting precursor.
Wherein " Na in system2S and H2The molar ratio of O is 1:H in 10~20 "2The mole of O is the crystallization water in system
The sum of with the mole of free water.
Inventor's research thinks that the preparation process of vulcanized sodium reacting precursor is merely not only the process for removing the crystallization water.And
It proposes：During wateriness sodium sulfide thermal dehydration, the crystallization water is heated is decomposed into free water first, H in free water+With N-
Electronegative oxygen in the amides compounds such as methyl pyrrolidone, which combines, forms hydrogen bond, realizes the solvent of N-Methyl pyrrolidone
Change, due to vulcanized sodium N-Methyl pyrrolidone solubility very little, the amides such as N-Methyl pyrrolidone are made by solvation
Class compound can be contacted with a large amount of vulcanized sodium, and electronegative oxygen in amides compound is made to continue to attract band in vulcanized sodium
There is the sodium ion of positive charge so as to form a kind of ternary complex of stable structure, i.e., so-called intermediate of the invention, among this
The formation of body makes the sulphion in vulcanized sodium with stronger negative electrical charge, therefore the intermediate passes through the vulcanization that dehydration obtains
Sodium reacting precursor is more prone to be combined that polycondensation reaction is promoted quickly to carry out with paracide in polycondensation reaction.
Ternary complex structure is as shown in Figure 1：
Therefore inventor thinks that the dehydration of wateriness sodium sulfide can be divided into two stages to understand, i.e. the shape of intermediate
Into stage and the removing stage of intermediate moisture.It is believed that free water plays crucial work in the forming process of intermediate
With, the complex of the amides compounds such as vulcanized sodium and NMP generation need to improve the activity of solvent by the hydrogen bond action of water, and
Stable ternary complex is formed, and the water in system must be free water when hydrogen bond action occurs.This puts us in the past simultaneously
It is unaware that.In traditional technique, the crystallization water that the formation of free water is practically due in wateriness sodium sulfide is thermally decomposed
It generates, and the crystallization water in wateriness sodium sulfide needs to absorb largely heat and could decompose to provide enough H for system+, this
Lead to that enough intermediates cannot be formed in the shorter reaction time in system, therefore just result in the extension of dewatering time, I
Think this be actually intermediate formed the time length caused by, therefore shorten wateriness sodium sulfide dewatering time actually
Key is to shorten the formation time of intermediate.
In the present invention, it inventors herein proposes and adds in water the mode of free water is provided for system, it is direct due to free water
It adds in, enough H is directly provided for system+, therefore need not wait for crystallization water decomposition that can meet the need that intermediate is formed
Will, form the time so as to play the role of shortening intermediate.
The purpose that the time is formed and shortens intermediate is realized by this programme, it is necessary to assure free water can carry in system
For enough H+, otherwise still need to wait for could generating after the crystallization water decomposes stabilization complex be just unlikely to influence follow-up polycondensation it is anti-
It should.It is demonstrated experimentally that as H in system2O (including the crystallization water and free water) and Na2The molar ratio of S is at least 10:It can reach when 1
Corresponding purpose, but adding in hypervolia can cause vulcanized sodium to be decomposed at high temperature reaction, make follow-up polycondensation reaction generation
It is abnormal.Test H in identity system2O (including the crystallization water and free water) and Na2The molar ratio of S should be controlled 10~20:1 model
In enclosing.
It should be noted that in this programme although the addition of water results in the step B intermediate water smokings and takes and suitably prolong
It is long, but its contribution to the shortening of intermediate formation stages time is more notable, and since also there are one after the completion of the water smoking
In systems, which also saves plenty of time and energy consumption, the water removal of traditional technological requirement is thorough for fixed free water, thus the time and
Energy all consumes greatly.
The dehydrating amount of mesosome system passes through verification experimental verification, in Liquid level when between 25~50%, system in stepb
Free water content have no adverse effect to the polycondensation reaction in later stage.
In the present invention, we can judge whether system has formed stabilization by the free water content in measure system
Ternary complex, since part water generates ternary complex, thus content of water in system than reaction before it is few, theoretically reduce
Water forms stable ternary complex when consistent with the molal quantity of vulcanized sodium；Experimental results demonstrate the first stage is usually anti-
It can ensure that stable ternary complex is formed after answering 30min.Production is controlled also with stronger using this standard
Operability.
In the present invention, entrainer used needs to select amides compound, such as formamide, acetamide, N- methyl formyls
Amine, n,N-Dimethylformamide, n,N-dimethylacetamide, 2-Pyrrolidone, hexamethyl phosphoramide, N-Methyl pyrrolidone
It can serve as the entrainer of the present invention.Preferably, entrainer of the N-Methyl pyrrolidone as the present invention is preferably selected.
As a further improvement on the present invention, the raw material by wateriness sodium sulfide, N-Methyl pyrrolidone, sodium hydroxide,
Sodium acetate in molar ratio 1:5~10:0.02:0.02 ratio composition.In the present solution, we add in the feed it is a certain amount of
Sodium hydroxide and sodium acetate, add in sodium hydroxide the purpose is to reduce vulcanized sodium there is a situation where aoxidizing, and add in sodium acetate
It is to reduce NMP in alkalinity and under conditions of heating there is a situation where hydrolyzing, while sodium acetate also serves as later stage polycondensation reaction
Third monomer.
As a further improvement on the present invention, the method for oxygen is in exclusion pre-reactor in step A：Into pre-reactor
Nitrogen is passed through to the gas phase in pre-reactor into line replacement.In addition to this, other modes that can also take are readily apparent that, such as
Air in pre-reactor is extracted out using high vacuum.
As a further improvement on the present invention, the dewatering described in step B is specially：The temperature of pre-reactor is increased
It is 0.05~0.095MPa to 190~210 DEG C, and using vacuum degree in vacuum pump control container, is then removed by the mode of distilling
Remove water extra in system.This programme is distilled under certain vacuum degree, is formed altogether with water because the process of dehydration is NMP
Object dehydration by evaporation is boiled, the purpose of vacuum is to reduce azeotropic mixture boiling point, energy saving and time.
In the program, during distillation dehydration, when pre-reactor liquid level drop to distillation before pre-reactor liquid level 25~
Stop heating when 50%.It has been recognised by the inventors that the water in ternary complex is just necessary, and ternary complex formed it is rear remaining
Free water is extra.Since water and NMP dissolve each other, have no idea except totally, control is to ensure to remain to certain liquid level
Remaining free water stops without having an adverse effect polycondensation reaction water removal, and for saving time and energy saving.Tradition
Technological requirement water removal it is thorough, so time and energy all consume it is especially big.It can also so say, water is added to form ternary complex
It has saved the time, the later stage no thoroughness of water removal also saves plenty of time and energy consumption.And since water and NMP can dissolve each other, lead to
The mode for crossing liquid level reduction carrys out the water content of control system, there is preferable operability in production.The reduction ratio of liquid level can root
Water content before being dehydrated according to system adjusts accordingly within this range.
The beneficial effects of the invention are as follows：1) preparation time of vulcanized sodium reacting precursor can be foreshortened to 2~3h by 4~6h,
More than 50% technique energy consumption is reduced wherein and accordingly, there is significant economic and environment-friendly value；2) scheme is implemented simple, conducive to
It is promoted in industry.
Description of the drawings
Fig. 1 is the ternary complex structure chart formed in wateriness sodium sulfide dehydration.
Specific embodiment
With reference to embodiment, the present invention is further described.
Embodiment one：
In the pre-reactor of 25L, three water vulcanized sodium, NMP (N-Methyl pyrrolidone), sodium hydroxide and sodium acetate are pressed
Molar ratio 1:5:0.02:0.02 ratio is added in pre-reactor, adds a certain amount of deionized water, controls deionized water
Addition ensure that the molar ratio of vulcanized sodium and water (including the crystallization water and free water) in system is 1:10, heating front opening is pre- anti-
Kettle is answered to stir, opens simultaneously nitrogen to the gas-phase space of pre-reactor into line replacement, time swap 10 minutes is then added using electricity
System temperature is raised to 150 DEG C by hot mode, this temperature to complete reaction is maintained to form stable ternary complex, is taken
30min obtains aqueous vulcanized sodium reacting precursor (i.e. intermediate).
Continue pre-reactor temperature to be raised to 190 DEG C with conduction oil, and be using vacuum pump control system vacuum degree
0.05MPa, then by distilling water extra in mode removing system, extra water leaves in gaseous form with NMP to react
System, condensed waste water enter solvent recovery unit, and uncooled gas passes through qualified discharge after Alkali absorption.Work as pre-reactor
Liquid level stops heating when falling to 50% before distilling, and takes 60min, obtains vulcanized sodium reacting precursor A.
Obtained vulcanized sodium reacting precursor A is pipelined to reaction kettle and carries out polycondensation reaction in accordance with the following methods, system
Obtain polyphenylene sulfide product A.Polyphenylene sulfide polycondensation process is as follows：
It first turns on polycondensation vessel to be stirred, the N-Methyl pyrrolidone measured is added in into polycondensation reaction before the reaction
Kettle is subsequently added into the vulcanized sodium reacting precursor A measured and paracide solution.
After the completion of charging, closed batch condensation polymerization reactor simultaneously carries out warming temperature by heating curve.After heating, reaction system
Polycondensation reaction, reaction time 6h are carried out under conditions of 260 DEG C of reaction temperature, pressure 1.1MPa.
Polyphenylene sulfide slurry is water-cooled to 100 DEG C through cooling after reaction, then opens baiting valve and passes through closed conduit
Polyphenylene sulfide slurry is put to slurry tank.Polyphenylene sulfide slurry is gathered by the processing steps such as subsequent separation, washing, dry
Diphenyl sulfide product A.
Embodiment two：
In the pre-reactor of 25L, by nine water vulcanized sodium, formamide in molar ratio 1:10 ratio is added to pre-reactor
In, a certain amount of deionized water is added, controlling the addition of deionized water ensures that vulcanized sodium and water are (including the crystallization water in system
And free water) molar ratio be 1:20, it is empty to the gas phase of pre-reactor to open simultaneously nitrogen for the pre-reactor stirring of heating front opening
Between system temperature is then raised to 180 DEG C using Electric heating, maintains this temperature extremely into line replacement, time swap 10 minutes
Reaction forms stable ternary complex completely, takes 40min, obtains aqueous vulcanized sodium reacting precursor (i.e. intermediate).
Continue pre-reactor temperature to be raised to 208 DEG C with conduction oil, and be using vacuum pump control system vacuum degree
0.08MPa, then by distilling water extra in mode removing system, extra water leaves instead in gaseous form with formamide
System is answered, condensed waste water enters solvent recovery unit, and uncooled gas passes through qualified discharge after Alkali absorption.Work as pre-reaction
Kettle liquid position stops heating when falling to 25% before distilling, and takes 120min, obtains vulcanized sodium reacting precursor B.
Obtained vulcanized sodium reacting precursor B is pipelined to reaction kettle and carries out polycondensation according to the method in embodiment one
Polyphenylene sulfide product B is made in reaction.
Embodiment three：
In the pre-reactor of 25L, by five water vulcanized sodium, 2-Pyrrolidone, sodium hydroxide in molar ratio 1:8:0.02
Ratio is added in pre-reactor, adds a certain amount of deionized water, is controlled the addition of deionized water and is ensured sulphur in system
The molar ratio for changing sodium and water (including the crystallization water and free water) is 1:15, the pre-reactor stirring of heating front opening opens simultaneously nitrogen
Gas to the gas-phase space of pre-reactor into line replacement, time swap 10 minutes, then using Electric heating by system temperature liter
To 160 DEG C, this temperature to complete reaction is maintained to form stable ternary complex, 30min is taken, obtains aqueous vulcanized sodium
Reacting precursor (i.e. intermediate).
Continue pre-reactor temperature to be raised to 200 DEG C with conduction oil, and be using vacuum pump control system vacuum degree
0.095MPa, then by distilling water extra in mode removing system, extra water and 2-Pyrrolidone are in gaseous form
Reaction system is left, condensed waste water enters solvent recovery unit, and uncooled gas passes through qualified discharge after Alkali absorption.When
Pre-reactor liquid level stops heating when falling to 30% before distilling, and takes 90min, obtains vulcanized sodium reacting precursor C.
Obtained vulcanized sodium reacting precursor C is pipelined to reaction kettle and carries out polycondensation according to the method in embodiment one
Polyphenylene sulfide products C is made in reaction.
Comparative example four：
In the pre-reactor of 25L, three water vulcanized sodium, NMP (N-Methyl pyrrolidone), sodium hydroxide and sodium acetate are pressed
Molar ratio 1:5:0.02:0.02 ratio is added in pre-reactor, and the pre-reactor stirring of heating front opening opens simultaneously nitrogen
To the gas-phase space of pre-reactor into line replacement, system temperature is then raised to by time swap 10 minutes using Electric heating
150 DEG C, this temperature to complete reaction is maintained to form stable ternary complex, takes 2h, before obtaining aqueous vulcanized sodium reaction
Body (i.e. intermediate).
Continue pre-reactor temperature to be raised to 190 DEG C with conduction oil, and be using vacuum pump control system vacuum degree
0.05MPa, then by distilling water extra in mode removing system, extra water leaves in gaseous form with NMP to react
System, condensed waste water enter solvent recovery unit, and uncooled gas passes through qualified discharge after Alkali absorption.Work as pre-reactor
Liquid level stops heating when falling to 50% before distilling, and takes 45min, obtains vulcanized sodium reacting precursor D.
Obtained vulcanized sodium reacting precursor D is pipelined to reaction kettle and carries out polycondensation according to the method in embodiment one
Polyphenylene sulfide product D is made in reaction.
Comparative example five：
In the pre-reactor of 25L, three water vulcanized sodium, NMP (N-Methyl pyrrolidone), sodium hydroxide and sodium acetate are pressed
Molar ratio 1:5:0.02:0.02 ratio is added in pre-reactor, adds a certain amount of deionized water, controls deionized water
Addition ensure that the molar ratio of vulcanized sodium and water (including the crystallization water and free water) in system is 1:5, heating front opening is pre- anti-
Kettle is answered to stir, opens simultaneously nitrogen to the gas-phase space of pre-reactor into line replacement, time swap 10 minutes is then added using electricity
System temperature is raised to 150 DEG C by hot mode, this temperature to complete reaction is maintained to form stable ternary complex, is taken
110min obtains aqueous vulcanized sodium reacting precursor (i.e. intermediate).
Continue pre-reactor temperature to be raised to 190 DEG C with conduction oil, and be using vacuum pump control system vacuum degree
0.05MPa, then by distilling water extra in mode removing system, extra water leaves in gaseous form with NMP to react
System, condensed waste water enter solvent recovery unit, and uncooled gas passes through qualified discharge after Alkali absorption.Work as pre-reactor
Liquid level stops heating when falling to 50% before distilling, and takes 60min, obtains vulcanized sodium reacting precursor E.
Obtained vulcanized sodium reacting precursor E is pipelined to reaction kettle and carries out polycondensation according to the method in embodiment one
Polyphenylene sulfide product E is made in reaction.
Comparative example six：
In the pre-reactor of 25L, three water vulcanized sodium, NMP (N-Methyl pyrrolidone), sodium hydroxide and sodium acetate are pressed
Molar ratio 1:5:0.02:0.02 ratio is added in pre-reactor, and the pre-reactor stirring of heating front opening opens simultaneously nitrogen
To the gas-phase space of pre-reactor into line replacement, system temperature is then raised to by time swap 10 minutes using Electric heating
190 DEG C, and be 0.05MPa using vacuum pump control system vacuum degree, then by distilling water extra in mode removing system,
Extra water leaves reaction system in gaseous form with NMP, and condensed waste water enters solvent recovery unit, uncooled gas
Body passes through qualified discharge after Alkali absorption.Stop heating after being dehydrated 90min, obtain vulcanized sodium reacting precursor F.
Obtained vulcanized sodium reacting precursor F is pipelined to reaction kettle and carries out polycondensation according to the method in embodiment one
Polyphenylene sulfide product F is made in reaction.
Table 1：Dewatering process takes the table of comparisons
Table 2：Polyphenylene sulfide product index detects table
Claims (6)
1. the preparation method of vulcanized sodium reacting precursor, includes the following steps in polyphenylene sulfide production：
A, it dissolves：Raw material is added in pre-reactor by a certain percentage, the raw material includes wateriness sodium sulfide and entrainer, described
Entrainer is amides compound；Into system plus water ensures Na in system2S and H2The molar ratio of O is 1:10~20, Ran Houpai
Except the oxygen in pre-reactor, mixture is heated later and to 150~180 DEG C and maintains the temperature at least 30min, obtains centre
Body；
B, it is dehydrated：The excessive moisture in intermediate is sloughed in distillation, obtains vulcanized sodium reacting precursor.
2. the preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production according to claim 1, it is characterised in that：Institute
It states entrainer and is selected from formamide, acetamide, N-METHYLFORMAMIDE, n,N-Dimethylformamide, n,N-dimethylacetamide, 2- pyrroles
One kind in pyrrolidone, hexamethyl phosphoramide, N-Methyl pyrrolidone.
3. the preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production according to claim 1, it is characterised in that：Institute
Raw material is stated by wateriness sodium sulfide, N-Methyl pyrrolidone, sodium hydroxide, sodium acetate in molar ratio 1:5~10:0.02:0.02
Ratio forms.
4. the preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production according to claim 1, it is characterised in that：Step
The method of oxygen is in exclusion pre-reactor in rapid A：Nitrogen is passed through into pre-reactor to put the gas phase in pre-reactor
It changes.
5. the preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production according to claim 1, it is characterised in that：Step
Suddenly the dewatering described in B is specially：The temperature of pre-reactor is increased to 190~210 DEG C, and utilize vacuum pump control container
Interior vacuum degree is 0.05~0.095MPa, then by distilling water extra in mode removing system.
6. the preparation method of vulcanized sodium reacting precursor in polyphenylene sulfide production according to claim 5, it is characterised in that：It steams
Evaporate in dehydration, when pre-reactor liquid level drop to distillation before pre-reactor liquid level 25~50% when stop heating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110818898A (en) * | 2019-11-22 | 2020-02-21 | 四川轻化工大学 | Method for dehydrating sodium sulfide dihydrate in polyphenylene sulfide production |
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