CN103275320A - Method for preparing linear high molecular weight polyphenylene sulfide by utilizing pre-desalting method - Google Patents
Method for preparing linear high molecular weight polyphenylene sulfide by utilizing pre-desalting method Download PDFInfo
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Abstract
The invention relates to a method for preparing linear high molecular weight polyphenylene sulfide by utilizing a pre-desalting method. The method comprises the steps of adding sodium sulfhydrate into NMP (N-methyl-2-pyrrolidone) dissolved with lithium chloride under the inert gas shielding, separating solid sodium chloride after reacting under the heating condition of 70-110 DEG C, obtaining an NMP solution of lithium hydrogen sulfide, continuing to heat to 150-190 DEG C till no hydrogen sulphide escapes, obtaining an NMP suspension of lithium sulfide, adding p-dichlorobenzene and a catalyzing amount of lithium hydroxide at a molar ratio of (0.95-1.1):1, performing and accomplishing polymerization reaction for generating a target product at 190-280 DEG C and 0.1-0.5 MPa, and collecting a precipitation product after cooling. The product is 284-289 DEG C in melting point, 50000-52000 in weight-average molecular weight, 2-3 in molecular weight distribution index, and less than 300ppm in chloride ion content. Since a great deal of sodium chloride is removed before the polymerization reaction, the method solves the problems that a product produced by the traditional method is high in sodium chloride content, and sodium chloride is difficult to remove to result in low quality of the product.
Description
Technical field
The present invention relates to a kind of improvement to the linear high molecular weight polyphenylene sulfide preparation method.
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.Though US Patent No. 5235032 has reported that a kind of is raw material with Sodium sulfhydrate and santochlor, NMP is solvent, is the polyphenylene sulfide that container prepares low impurity content with the titanium reactor, but its method cost height not only, and the content of sodium ion is still higher, the degree of depth of still needing purifying.
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 before polyreaction, be about to sodium-chlor and remove, solved the problems referred to above satisfactorily.
Desalination process prepares the method for linear high molecular weight polyphenylene sulfide before the present invention, is with the N-Methyl pyrrolidone reaction medium, and Sodium sulfhydrate and santochlor are that raw material carries out the improvement on the polyreaction basis.Specifically undertaken by following step:
1': at rare gas element, be preferably nitrogen environment protection commonly used down, the Sodium sulfhydrate adding be dissolved with in the N-Methyl pyrrolidone of lithium chloride, after reaction under 70 ~ 110 ℃ of heating conditions, separate the sodium-chlor solid substance, obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride;
2': with the N-Methyl pyrrolidone solution of above-mentioned sulphur lithium hydride, under protection of inert gas, be heated to 150 ~ 190 ℃, do not overflow to there being hydrogen sulfide, obtain the N-Methyl pyrrolidone suspension of lithium sulfide;
3': the santochlor raw material is added the N-Methyl pyrrolidone suspension of going up the step lithium sulfide, in the presence of the catalytic amount lithium hydroxide, carry out under 190 ~ 280 ℃ of temperature and 0.1 ~ 0.5MPa pressure condition and finish polyreaction, cooling back collecting precipitation product obtains target product.Lithium sulfide wherein and the mol ratio of santochlor are 0.95 ~ 1.1:1.
Said protection of inert gas in the above-mentioned preparation process is preferably under the nitrogen environment commonly used and protects.
On the aforesaid method basis, can also be separately or the further preferred embodiment that adopts in the arbitrary combination mode comprise:
The temperature of reaction in said 1' step is preferably 75-95 ℃.
The temperature of reaction in said 2' step is preferably 170 ~ 190 ℃.
The lithium sulfide in said 3' step and the mol ratio of santochlor are preferably 0.95 ~ 1:1.
The polyreaction in said 3' step is under said pressure, be preferably in two steps and carry out: under 0.1 ~ 0.2MPa pressure condition, carried out prepolymerization reaction 1 ~ 3 hour at 190 ~ 220 ℃ earlier, be warming up to 220 ~ 280 ℃ then, continuation was reacted under 0.2 ~ 0.5MPa pressure condition 2 ~ 4 hours, finished polyreaction.
When adopting said two-stage polymerization to react, the preferable reaction temperature that second step was finally finished polyreaction is 250 ~ 280 ℃.
Be further to improve the crystallization yield of product, a kind of preferred mode is, after said polyreaction is finished, be cooled to≤120 ℃ after, in reactant, add the water mixing that comprises normal temperature (as 25 ~ 30 ℃) lesser temps of etc.ing, collect cooled precipitated product.。
Among the above-mentioned preparation method, after the said 3' step, polyreaction was finished, to collected precipitated product, can be 60-80% with the N-Methyl pyrrolidone part by weight respectively, after being preferably 70% the aqueous solution and water washing, 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.
Experimental result shows, the above-mentioned linear polyphenylene sulfide product for preparing of the present invention, and outward appearance is the pure white powder, 284 ~ 289 ℃ of fusing points, weight-average molecular weight is 50,000 ~ 52,000, and molecular weight distributing index is 2 ~ 3, and chloride ion content is less than 300ppm.Preparation method's circulation ratio and good stability that the present invention is above-mentioned.Because in preparation method of the present invention, be actually lithium sulfide and santochlor and carry out polycondensation, its characteristics and superiority are, lithium sulfide is on the one hand as the reactive polymeric raw material, also has corresponding self-catalysis simultaneously, under the lithium hydroxide auxiliary catalysis effect that further adds cooperates, be conducive to realize and guarantee the high molecular of product and narrow molecular weight distribution.Because aforesaid method of the present invention just removes a large amount of sodium-chlor before carrying out polyreaction, not only thoroughly solved the problem that is subjected to the sodium-chlor puzzlement in the traditional method, but also 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, greatly improve the quality of product.
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
The abundant stirring and dissolving of the lithium chloride of 424g in the N-Methyl pyrrolidone of 3000g, is added the abundant stirring suspension of Sodium sulfhydrate of 560g, again in N
2Under the atmospheric condition, slowly be heated to 80 ℃, reacted 3 hours, filter the N-Methyl pyrrolidone solution of sulphur lithium hydride.Filter cake sodium-chlor washs 3 times with the hot N-Methyl pyrrolidone of 45 ℃ of 1000g, namely gets high pure white sodium chloride crystal 570g.
At N
2Under the atmospheric condition, the N-Methyl pyrrolidone solution of the above-mentioned sulphur lithium hydride that obtains is heated to 150 ℃, reacts to the system no hydrogen sulfide and overflow, obtain the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas absorbs with alkali lye.
In the N-Methyl pyrrolidone suspension of the above-mentioned lithium sulfide that obtains, add 735g santochlor and 36g lithium hydroxide, be warming up to 220 ℃, in autoclave, (be self pressure by N-Methyl pyrrolidone self pressure of producing of vaporization under this temperature, be generally 0.1-0.2Mpa) prepolymerization reaction 2 hours under the condition, be warming up to 260 ℃ then, continuation (was generally under 0.2 ~ 0.5MPa) condition reaction 3 hours, and finished polyreaction at self pressure.Reacting rear material is cooled to 120 ℃, and the water " cold shock " that adds the 1500g room temperature is sized mixing, again cooling, crystalline deposit, filter precipitated product 1500g 70%(w) N-Methyl pyrrolidone solution washing 3 times, distilled water wash 4 times, the dry linear polyphenylene sulfide rosin products 478g that gets, be the pure white powder, 286 ℃ of fusing points, weight-average molecular weight is 510000, molecular weight distributing index is 2.15, chloride ion content 291ppm.
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 polyphenylene sulfide of 71-73 etc.) reporting (PPS) resin shows that this product is linear polyphenylene sulfide.
Filtrate behind aforementioned " cold shock " sedimentation and filtration and 70%N-methyl-2-pyrrolidone aqueous solution washing lotion merge, and hydrochloric acid is regulated pH to 8, and distillation dewaters, and gets the N-Methyl pyrrolidone solution 5952g of lithium chloride, can return sulphur lithium hydride preparation process and recycle.
Embodiment 2
The abundant stirring and dissolving of the lithium chloride of 445g in the N-Methyl pyrrolidone of 4000g, is added the abundant stirring suspension of Sodium sulfhydrate of 560g, again in N
2Under the atmospheric condition, slowly be heated to 80 ℃, reacted 3 hours, filter the N-Methyl pyrrolidone solution of sulphur lithium hydride.Filter cake sodium-chlor washs 2 times with the hot N-Methyl pyrrolidone of 30 ℃ of 1500g, namely gets high pure white sodium chloride crystal 560g.
At N
2Under the atmospheric condition, the N-Methyl pyrrolidone solution of the above-mentioned sulphur lithium hydride that obtains is heated to 190 ℃, reacts to the system no hydrogen sulfide and overflow, obtain the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas absorbs with alkali lye.
With the santochlor of 735g, the lithium hydroxide of 30g joins in the N-Methyl pyrrolidone suspension of above-mentioned lithium sulfide, is warming up to 190 ℃ of prepolymerization reactions 3 hours under self pressure condition.Be warming up to 220 ℃ after reaction finishes, continued under self pressure condition polyreaction 4 hours.Reaction is cooled to 120 ℃ after finishing, and the water " cold shock " that adds the 2000g room temperature is sized mixing, cooling again, crystalline deposit filters, filter cake 2000g 70%N-methyl-2-pyrrolidone solution washing 2 times, distilled water wash 6 times, the dry polyphenylene sulfide resin fat prod 465g that gets, outward appearance is the pure white powder, 284.5 ℃ of fusing points, weight-average molecular weight is 50100, and molecular weight distributing index is 2.35, chloride ion content 295ppm.Filtrate and 70%N-methyl-2-pyrrolidone aqueous solution washing lotion that previous reaction is finished to obtain after " cold shock " filters merge, regulate pH to 7 with hydrochloric acid, distillation dewaters, and gets the N-Methyl pyrrolidone solution 6536g of lithium chloride, can be back to sulphur lithium hydride preparation process and recycle after forming adjustment.
Embodiment 3
The abundant stirring and dissolving of the lithium chloride of 430g in the N-Methyl pyrrolidone of 5000g, is added the abundant stirring suspension of Sodium sulfhydrate of 560g, again in N
2Slowly be heated to 80 ℃ under the atmospheric condition, reacted 3 hours, filter the N-Methyl pyrrolidone solution of sulphur lithium hydride.Filter cake sodium-chlor washs 3 times with 1000g50 ℃ hot N-Methyl pyrrolidone, namely gets high pure white sodium chloride crystal 565g.
At N
2Under the atmospheric condition, the N-Methyl pyrrolidone solution of above-mentioned sulphur lithium hydride is heated to 170 ℃, reacts to the system no hydrogen sulfide and overflow, make the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas absorbs with alkali lye.
With the santochlor of 735g, the lithium hydroxide of 40g adds in the N-Methyl pyrrolidone suspension of above-mentioned lithium sulfide, is warming up to 220 ℃, and the prepolymerization reaction is 1 hour under self pressure condition.Be warming up to 270 ℃ after reaction finishes, under self pressure condition, continue reaction 2 hours, finish polyreaction.Reaction is cooled to 120 ℃ after finishing, and the water " cold shock " that adds the 1500g room temperature is sized mixing, cooling again, and crystalline deposit filters.Filter cake 1500g 70%N-methyl-2-pyrrolidone solution washing 3 times are used distilled water wash 6 times, drying again, get linear polyphenylene sulfide product 470g, outward appearance is the pure white powder, 289 ℃ of fusing points, weight-average molecular weight is 514000, and molecular weight distributing index is 2.56, chloride ion content 285ppm.Filtrate and 70%N-methyl-2-pyrrolidone aqueous solution washing lotion that previous reaction is finished to obtain after " cold shock " filters merge, and hydrochloric acid is regulated pH to 7.5, and distillation dewaters, and gets the N-Methyl pyrrolidone solution 7752g of lithium chloride.This solution can be back to sulphur lithium hydride preparation process and recycle after forming adjustment.
Claims (10)
1. preceding desalination process prepares the method for linear high molecular weight polyphenylene sulfide, in the N-Methyl pyrrolidone reaction medium, is that raw material is prepared through polyreaction with Sodium sulfhydrate and santochlor, it is characterized in that being undertaken by following step:
1': under protection of inert gas, be preferably under the nitrogen protection commonly used, the Sodium sulfhydrate adding be dissolved with in the N-Methyl pyrrolidone of lithium chloride, after reaction under 70 ~ 110 ℃ of heating conditions, separate the sodium-chlor solid substance, obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride;
2': with the N-Methyl pyrrolidone solution of above-mentioned sulphur lithium hydride, under protection of inert gas, be heated to 150 ~ 190 ℃, do not overflow to there being hydrogen sulfide, obtain the N-Methyl pyrrolidone suspension of lithium sulfide;
3': the santochlor raw material is added the N-Methyl pyrrolidone suspension of going up the step lithium sulfide, in the presence of the catalytic amount lithium hydroxide, 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 0.95 ~ 1.1:1.
2. the method for claim 1 is characterized in that the temperature of reaction in said 1' step is 75-95 ℃.
3. the method for claim 1 is characterized in that the temperature of reaction in said 2' step is 170 ~ 190 ℃.
4. the method for claim 1 is characterized in that the mol ratio of lithium sulfide and santochlor is 0.95 ~ 1:1 in the said 3' step reaction.
5. as the described method of one of claim 1 to 4, it is characterized in that the lithium sulfide in said 3' step and the mol ratio of santochlor are 1
:1.
6. as the described method of one of claim 1 to 4, it is characterized in that said 3' goes on foot polyreaction and carries out in two steps under said pressure, earlier under 0.1 ~ 0.2MPa pressure condition, carried out prepolymerization reaction 1 ~ 3 hour at 190 ~ 220 ℃, be warming up to 220 ~ 280 ℃ then, continuation was reacted under 0.2 ~ 0.5MPa pressure condition 2 ~ 4 hours, finished polyreaction.
7. method as claimed in claim 6 is characterized in that the final polyreaction in said second step is carried out under 250 ~ 280 ℃ of temperature.
8. as the described method of one of claim 1 to 4, after the polyreaction that it is characterized in that the said 3' step is finished, be cooled to≤120 ℃ after, add normal-temperature water in the reactant and mix, collect cooled precipitated product.
9. as the described method of one of claim 1 to 4, it is characterized in that precipitated product that the said 3' step collects is the aqueous solution and water washing of 60-80% with the N-Methyl pyrrolidone part by weight respectively after, drying.
10. method as claimed in claim 9 is characterized in that the part by weight of the aqueous solution of the N-Methyl pyrrolidone of said 3' step washing usefulness is 70%.
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Cited By (5)
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| 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 |
| CN105254889A (en) * | 2015-11-11 | 2016-01-20 | 成都惠恩精细化工有限责任公司 | High-purity linear polyarylene sulfide and synthesis method and application thereof |
| CN107964098A (en) * | 2017-11-29 | 2018-04-27 | 中国石油化工股份有限公司 | The method and device of desalination in a kind of polyphenylene sulfide synthesis |
| WO2018120954A1 (en) * | 2016-12-30 | 2018-07-05 | 浙江新和成特种材料有限公司 | Polyphenylene sulfide having low chlorine content, preparation method therefor, resin composition, and formed body |
| CN114590825A (en) * | 2022-02-28 | 2022-06-07 | 湖北金泉新材料有限公司 | Purification method and purification equipment for sodium-containing lithium chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN105254889A (en) * | 2015-11-11 | 2016-01-20 | 成都惠恩精细化工有限责任公司 | High-purity linear polyarylene sulfide and synthesis method and application thereof |
| CN105254889B (en) * | 2015-11-11 | 2017-07-18 | 成都惠恩精细化工有限责任公司 | A kind of linear poly arylidene thio-ester of high-purity and its synthetic method and application |
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| KR20190095102A (en) * | 2016-12-30 | 2019-08-14 | 저지앙 엔에이치유 스페셜 머티어리얼스 컴퍼니 리미티드 | Low chlorine polyphenylene sulfides and methods for their preparation, resin compositions and shaped bodies |
| KR102239311B1 (en) | 2016-12-30 | 2021-04-12 | 저지앙 엔에이치유 스페셜 머티어리얼스 컴퍼니 리미티드 | Low chlorine content polyphenylene sulfide and its preparation method, resin composition and molded article |
| CN107964098A (en) * | 2017-11-29 | 2018-04-27 | 中国石油化工股份有限公司 | The method and device of desalination in a kind of polyphenylene sulfide synthesis |
| CN107964098B (en) * | 2017-11-29 | 2020-03-27 | 中国石油化工股份有限公司 | Method and device for desalting in polyphenylene sulfide synthesis |
| CN114590825A (en) * | 2022-02-28 | 2022-06-07 | 湖北金泉新材料有限公司 | Purification method and purification equipment for sodium-containing lithium chloride |
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