CN103289093A - Method for preparing linear high molecular weight polyphenylene sulfide - Google Patents
Method for preparing linear high molecular weight polyphenylene sulfide Download PDFInfo
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- CN103289093A CN103289093A CN2013102713704A CN201310271370A CN103289093A CN 103289093 A CN103289093 A CN 103289093A CN 2013102713704 A CN2013102713704 A CN 2013102713704A CN 201310271370 A CN201310271370 A CN 201310271370A CN 103289093 A CN103289093 A CN 103289093A
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Abstract
The invention provides a method for preparing linear high molecular weight polyphenylene sulfide. N-methyl-2-pyrrolidone is used as a reaction medium, and polymerization reaction between lithium sulfide which is dispersed and suspends in the reaction medium and paradichlorobenzene for generating a target product is performed and finished at the temperature of between 190 and 280 DEG C and the pressure of between 0.1 and 0.5MPa in the presence of catalytic amounts of lithium hydroxide; and the precipitate product is collected after the target product is cooled, wherein the molar ratio between the lithium sulfide to the paradichlorobenzene is 1: 1. In the method, sodium ions are not introduced, the content of chlorine ions can be less than 200ppm, and the molecular weight distribution index of the product linear high molecular weight polyphenylene sulfide is between 2 and 3, so that the product quality can be improved. The method is good in stability and reproducibility, and can be used for fundamentally solving the problems of low controllability and reproducibility, poor environment friendliness of the production process, unstable product quality, wide molecular weight distribution, hard refining of massive side product sodium chloride, low additional value and the like due to the fact that the impurities in inorganic salt, in particular sodium chloride, in the product are high in content and difficult to remove in the traditional method.
Description
Technical field
The present invention relates to a kind of preparation method to linear high molecular weight polyphenylene sulfide.
Background technology
Polyphenylene sulfide (PPS) is polyphenylene sulfide, claim poly-phenylene thioether again, be the important chemical engineering plastics, it is the polyoxymethylene (POM) that continues, polycarbonate (PC), polyamide (PA), polybutylene terephthalate (PBT), and the sixth-largest engineering plastics behind the Noryl (MPPO), have good high temperature resistant, corrosion-resistant, radiation hardness, fire-retardant, balanced physical and mechanical properties and fabulous dimensional stability and good characteristics such as electrical property, be widely used as structural macromolecular material, by filling, be widely used as special engineering plastics after the modification, also can be made into various functional films, coating and matrix material are at electronic apparatus, aerospace, succeed and use in fields such as automobile transportation.
The traditional method of industrial production of linear high molecular weight polyphenylene sulfide is to be main raw material with sodium sulphite and santochlor, and lithium chloride is catalyzer, at the NMP(N-methyl-2-pyrrolidone) do to make through high-temperature high-voltage reaction under the condition of solvent.The subject matter that this method exists, the one, the controllability of technology and poor reproducibility, unstable product quality can only rely on subsequent analysis to classify; The 2nd, product of poor quality, molecular weight distribution is wide, is difficult to reach the requirement that high demand is used; The 3rd, polyphenylene sulfide in polymerization process to the inorganic salt impurity in the reaction system, the parcel of a large amount of sodium-chlor of especially separating out, make these impurity be difficult to be removed, cause its content height in the polyphenylene sulfide product, cause product seriously corroded to equipment in the following process process; The 4th, the feature of environmental protection of production technique does not pass a test, and produces a large amount of by product sodium-chlor in the production process and is difficult to make with extra care, and is difficult to after the separation utilize, and added value is low, and is low inferior to the recovery utilization rate of catalyzer and solvent.
Summary of the invention
At above-mentioned situation, the invention provides a kind of novel method for preparing linear high molecular weight polyphenylene sulfide, can address the above problem satisfactorily.
The present invention prepares the method for linear high molecular weight polyphenylene sulfide, be to be reaction medium with the N-Methyl pyrrolidone, by dispersion suspension in reaction medium lithium sulfide and santochlor in the presence of the lithium hydroxide of catalytic amount, under the condition of 190-280 ℃ of temperature and 0.1-0.5MPa pressure, carry out and finish the polyreaction of generation target product, cooling back collecting precipitation product, wherein the mol ratio of lithium sulfide and santochlor is 1
:1.
On the aforesaid method basis, wide for overcoming the step molecular weight distribution that easily causes of direct polymerization, though and adopt the good but problem such as complexity comparatively on the operational requirement of ladder-elevating temperature mode effect, a kind of preferred mode, be that said polyreaction is carried out in two steps: under 190-220 ℃ and 0.1-0.2Mpa condition, carried out prepolymerization reaction 1-3 hour earlier, be warming up to 220-280 ℃ then, continue under 0.2-0.5Mpa, to react 2-4 hour, finish polyreaction.
Wherein, the final polyreaction in second step is further preferably carried out under 250-280 ℃ of temperature in the above-mentioned two-step reaction mode.
Among the above-mentioned preparation method, for further improving the degree of crystallinity of product, a kind of preferred mode is, after said polyreaction is finished, be cooled to≤120 ℃ after, add the water mixing that comprises normal temperature (as the 25-30 ℃) lesser temps of etc.ing in the reactant, collect cooled precipitated product.
After polyreaction is finished, to collected precipitated product, can be respectively through the part by weight of N-Methyl pyrrolidone be 60-80%, be preferably 70% the aqueous solution and water washing after, drying is in order to remove and reclaim the catalyzer lithium hydroxide as far as possible.By the detection to the product fusing point, can check and judge the removal situation of impurity and the quality of product.Reaction solution after precipitated product collected and the washing lotion of washed product can merge aftertreatment, reclaim wherein lithium chloride and composition such as N-Methyl pyrrolidone, for reusing.
The lithium sulfide of one of said raw material among the above-mentioned preparation method of the present invention, except can by currently reported/and the variety of way of using obtains, a kind of can linking with the above-mentioned preparation method of the present invention and the optimal way that is conducive to operate continuously is:
1': under 70-110 ℃ of heating condition, by the lithium hydroxide and the hydrogen sulfide reaction that are scattered in the N-Methyl pyrrolidone, obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride.This step Heating temperature is unsuitable too high, in order to avoid the sulphur lithium hydride that generates decomposes.By controlling to the feeding amount of hydrogen sulfide and/or to the detection of sulphur hydrogen radical content in the reaction system, can understand and control the carrying out of reaction;
2': at rare gas element, be preferably nitrogen environment protection commonly used down, the N-Methyl pyrrolidone reactant that was contained the sulphur lithium hydride the last step is heated to no hydrogen sulfide at 150-190 ℃ and overflows, and obtains the N-Methyl pyrrolidone suspension of Containing Sulfur lithium.The protection of rare gas element is conducive to avoid the oxygenizement because of air to cause generating impurity such as Lithium Sulphate.
In the preparation method of above-mentioned lithium sulfide, can also be further separately or the optimal way of uniting employing comprise:
The temperature of reaction in said 1' step is 70-90 ℃;
The temperature of reaction in said 2' step is 170-190 ℃.
Experimental result shows, the above-mentioned linear polyphenylene sulfide product for preparing of the present invention, and outward appearance is the pure white powder, and fusing point is 284-289 ℃, and weight-average molecular weight can reach 50,000-52, and 000, molecular weight distributing index can reach 2-3.Preparation method's circulation ratio and good stability that the present invention is above-mentioned, adopting lithium sulfide is that raw material has not only been abandoned traditional sodium sulphite fully, its characteristics and superiority also are embodied in, lithium sulfide is in as reaction raw materials, can also have corresponding self-catalysis, under the lithium hydroxide auxiliary catalysis effect that further adds cooperates, be conducive to realize and guaranteed the high molecular of product and narrow molecular weight distribution.And owing to do not have the introducing of sodium ion fully in the preparation process, thereby thoroughly solved the problem that is subjected to the sodium-chlor puzzlement in the traditional method, and greatly reduced the content of chlorion in the product.Because under reaction conditions, be mainly derived from the chlorion of reaction raw materials santochlor, be that the lithium chloride form that is dissolved in fully in the N-Methyl pyrrolidone exists, can not separate out, therefore the polyphenylene sulfide that generates is enclosed with the lithium chloride of crystal form separating out Shi Buhui, lithium chloride can be removed (solubleness of lithium chloride in 25 ℃ of water is 67g, far above the 36g of solubleness in 25 ℃ of water of the sodium-chlor that generates in the traditional method) by corresponding washing.Therefore the content of chlorion can greatly improve the quality of product less than 200ppm in the linear polyphenylene sulfide product of method for preparing of the present invention.
Embodiment by the following examples is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Description of drawings
Fig. 1 is the Infrared spectroscopy figure of the linear polyphenylene sulfide rosin products of the inventive method preparation.
Embodiment
Embodiment 1
The abundant stirring suspension of the lithium hydroxide of 240g in the N-Methyl pyrrolidone of 1500g, is fed hydrogen sulfide, slowly be heated to 70 ℃, reacted 4 hours, obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride.With the N-Methyl pyrrolidone solution of the sulphur lithium hydride that obtains, at N
2Be heated to 150 ℃ under the atmospheric condition, react to the system no hydrogen sulfide and overflow, obtain the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas absorbs with alkali lye.
The santochlor that adds 735g in the N-Methyl pyrrolidone suspension of the above-mentioned Containing Sulfur lithium that obtains, the lithium hydroxide of 40g, be warming up to 220 ℃, pressure (self pressure that in autoclave, is produced by N-Methyl pyrrolidone self vaporization under this temperature, be generally 0.1-0.2Mpa) prepolymerization reaction 2 hours under the condition, be warming up to 260 ℃ after the end again, continue under self pressure condition (being generally 0.2-0.5Mpa) and carried out polyreaction 3 hours.Reaction is cooled to 120 ℃ after finishing, and the water " cold shock " that adds the 1500g room temperature is sized mixing, cooling again, filter filter cake 1500g70%N-methyl-2-pyrrolidone solution washing 3 times, distilled water wash 4 times, the dry linear polyphenylene sulfide rosin products 486g that gets, outward appearance is the pure white powder, 286 ℃ of fusing points, and weight-average molecular weight is 51000, molecular weight distributing index is 2.15, chloride ion content 191ppm.
With the sample preparation of KBr compressing tablet, place ThermoFisher Nicolet 6700 infrared spectrometers to scan then gained linear polyphenylene sulfide rosin products, scanning resolution is 4 cm
-1, the result as shown in Figure 1.By the results of IR of Fig. 1 as seen: 1590cm
-1, 1470cm
-1, 1390cm
-1Be the skeletal vibration absorption peak of phenyl ring, medium tenacity spike 1090cm
-1Be Ar-S vibration on the aromatic ring, 1905 cm
-1～1700 cm
-1Several weak absorption peaks are C-H out-of-plane vibration frequency multiplication and sum of fundamental frequencies peaks on 1, the 4-disubstituted benzenes ring, 818cm
-1Strong absorption peak is C-H out-of-plane deformation vibration absorption peak on 1, the 4-disubstituted benzenes ring.This infrared spectrum and document (Li Wengang etc., " Infrared spectroscopy of thermal treatment polyphenylene sulfide ", analysis and test, 2012,35 (2): the infared spectrum unanimity of the linear PPS resin of 71-73 etc.) reporting shows that this product is linear polyphenylene sulfide.
Embodiment 2
The abundant stirring suspension of the lithium hydroxide of 245g in the N-Methyl pyrrolidone of 2500g, is fed hydrogen sulfide, slowly be heated to 90 ℃, reacted 3 hours, obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride.With the N-Methyl pyrrolidone solution of the sulphur lithium hydride that obtains, at N
2Be heated to 190 ℃ under the atmospheric condition, react to the system no hydrogen sulfide and overflow, obtain the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas absorbs with alkali lye.
The santochlor that adds 735g in the N-Methyl pyrrolidone suspension of above-mentioned lithium sulfide, the lithium hydroxide of 36g is warming up to 220 ℃, and the prepolymerization reaction is 1 hour under self pressure condition, be warming up to 270 ℃ after the end again, continue under self pressure condition, to proceed polyreaction 2 hours.Reaction is cooled to 120 ℃ after finishing, and adds 1500g water " cold shock " and sizes mixing, cooling again, filter filter cake 2000g70%N-methyl-2-pyrrolidone solution washing 2 times, distilled water wash 5 times, the dry linear polyphenylene sulfide rosin products 476g that gets, outward appearance is the pure white powder, 284 ℃ of fusing points, and weight-average molecular weight is 50200, molecular weight distributing index is 2.15, chloride ion content 194ppm.
Embodiment 3
The abundant stirring suspension of the lithium hydroxide of 252g in the N-Methyl pyrrolidone of 2000g, is fed hydrogen sulfide, slowly be heated to 110 ℃, reacted 2 hours, obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride.With the N-Methyl pyrrolidone solution of the sulphur lithium hydride that obtains, at N
2Be heated to 180 ℃ under the atmospheric condition, react to the system no hydrogen sulfide and overflow, obtain the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas absorbs with alkali lye.
Add the santochlor of 735g and the lithium hydroxide of 30g in the N-Methyl pyrrolidone suspension of above-mentioned lithium sulfide, be warming up to 190 ℃, the prepolymerization reaction is 3 hours under self pressure condition.Be warming up to 220 ℃ again after reaction finishes, under self pressure condition, proceeded polyreaction 4 hours.Reaction is cooled to 120 ℃ after finishing, and adds 2000g water " cold shock " and sizes mixing, cooling again, filter filter cake 1500g70%N-methyl-2-pyrrolidone solution washing 3 times, distilled water wash 6 times, the dry polyphenylene sulfide resin fat prod 490g that gets, outward appearance is the pure white powder, 289 ℃ of fusing points, and weight-average molecular weight is 51700, molecular weight distributing index is 2.13, chloride ion content 195ppm.
Claims (10)
1. the method for preparing linear high molecular weight polyphenylene sulfide, it is characterized in that with the N-Methyl pyrrolidone being reaction medium, by dispersion suspension in reaction medium lithium sulfide and santochlor in the presence of the lithium hydroxide of catalytic amount, under 190-280 ℃ of temperature and 0.1-0.5Mpa pressure condition, carry out and finish the polyreaction of generation target product, cooling back collecting precipitation product, wherein the mol ratio of lithium sulfide and santochlor is 1
:1.
2. the method for claim 1, the mol ratio that it is characterized in that said lithium sulfide and santochlor is 1
:1.
3. the method for claim 1, it is characterized in that polyreaction carries out in two steps under said pressure, under 190-220 ℃ and 0.1-0.2Mpa condition, carried out prepolymerization reaction 1-3 hour earlier, be warming up to 220-280 ℃ then, continuation was reacted 2-4 hour under 0.2-0.5Mpa, finished polyreaction.
4. method as claimed in claim 3 is characterized in that the final polyreaction in said second step is carried out under 250-280 ℃ of temperature.
5. the method for claim 1, it is characterized in that said polyreaction is finished after, be cooled to≤120 ℃ after, add normal-temperature water in the reactant and mix, collect cooled precipitated product.
6. the method for claim 1 is characterized in that the precipitated product of collecting is 60-80% with the N-Methyl pyrrolidone part by weight respectively, be preferably 70% the aqueous solution and water washing after, drying.
7. as the described method of one of claim 1 to 6, it is characterized in that the raw material lithium sulfide of said polyreaction, obtained by following manner:
1': under 70-110 ℃ of heating condition, by the lithium hydroxide and the hydrogen sulfide reaction that are scattered in the N-Methyl pyrrolidone, obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride;
2': under protection of inert gas, the N-Methyl pyrrolidone reactant that the last step is contained the sulphur lithium hydride is heated to no hydrogen sulfide effusion at 150-190 ℃, obtains the N-Methyl pyrrolidone suspension of Containing Sulfur lithium.
8. method as claimed in claim 7 is characterized in that the temperature of reaction in said 1' step is 70-90 ℃.
9. method as claimed in claim 7 is characterized in that the temperature of reaction in said 2' step is 170-190 ℃.
10. method as claimed in claim 7 is characterized in that said 2' step reactionlessness gas shield is the protection of nitrogen environment.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103552990A (en) * | 2013-10-15 | 2014-02-05 | 四川宝利丰科技有限公司 | Production method of high-purity lithium sulfide |
| CN106750299A (en) * | 2017-01-13 | 2017-05-31 | 四川中科兴业高新材料有限公司 | A kind of preparation method of inexpensive polyphenylene sulfide |
| CN111342121A (en) * | 2020-02-10 | 2020-06-26 | 江苏大学 | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| CN111864272A (en) * | 2020-06-09 | 2020-10-30 | 江苏大学 | High-safety volume energy density quasi-solid lithium ion battery and manufacturing method thereof |
| WO2021098820A1 (en) * | 2019-11-21 | 2021-05-27 | 江苏大学 | Pre-lithiated polyphenylene sulfide, polyphenylene sulfide solid-state electrolyte membrane, battery electrode plate, quasi-solid-state lithium-ion battery, and method for manufacture thereof |
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| US4064114A (en) * | 1975-05-27 | 1977-12-20 | Phillips Petroleum Company | Production of arylene sulfide polymers |
| CN1500111A (en) * | 2001-03-30 | 2004-05-26 | ���ŷ���ʯ�Ͳ�ҵ���Ի����� | Process for continuous prodn. of polyarylene sulfide |
| CN1703446A (en) * | 2002-10-10 | 2005-11-30 | 出光兴产株式会社 | Method for producing polyarylene sulfide resin |
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Patent Citations (3)
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| US4064114A (en) * | 1975-05-27 | 1977-12-20 | Phillips Petroleum Company | Production of arylene sulfide polymers |
| CN1500111A (en) * | 2001-03-30 | 2004-05-26 | ���ŷ���ʯ�Ͳ�ҵ���Ի����� | Process for continuous prodn. of polyarylene sulfide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103552990A (en) * | 2013-10-15 | 2014-02-05 | 四川宝利丰科技有限公司 | Production method of high-purity lithium sulfide |
| CN106750299A (en) * | 2017-01-13 | 2017-05-31 | 四川中科兴业高新材料有限公司 | A kind of preparation method of inexpensive polyphenylene sulfide |
| WO2021098820A1 (en) * | 2019-11-21 | 2021-05-27 | 江苏大学 | Pre-lithiated polyphenylene sulfide, polyphenylene sulfide solid-state electrolyte membrane, battery electrode plate, quasi-solid-state lithium-ion battery, and method for manufacture thereof |
| US11289737B2 (en) | 2019-11-21 | 2022-03-29 | Jiangsu University | Pre-lithiated polyphenylene sulfide, polyphenylene sulfide-based solid electrolyte membrane, battery electrode sheet, quasi-solid-state lithium ion battery and method for manufacturing same |
| CN111342121A (en) * | 2020-02-10 | 2020-06-26 | 江苏大学 | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| CN111342121B (en) * | 2020-02-10 | 2022-03-11 | 江苏镇江固利纳新能源科技合伙企业(有限合伙) | Pre-lithiated polyphenylene sulfide with high solid lithium solubility, and preparation method and application thereof |
| CN111864272A (en) * | 2020-06-09 | 2020-10-30 | 江苏大学 | High-safety volume energy density quasi-solid lithium ion battery and manufacturing method thereof |
| CN111864272B (en) * | 2020-06-09 | 2022-04-26 | 江苏大学 | High-safety volume energy density quasi-solid lithium ion battery and manufacturing method thereof |
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Application publication date: 20130911 |