CN103275320B - Front desalination process prepares the method for linear high molecular weight polyphenylene sulfide - Google Patents
Front desalination process prepares the method for linear high molecular weight polyphenylene sulfide Download PDFInfo
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Abstract
Front desalination process prepares the method for linear high molecular weight polyphenylene sulfide.Under protection of inert gas, added by Sodium sulfhydrate and be dissolved with in the NMP of lithium chloride, under 70 ~ 110 DEG C of heating conditions after reaction, Isolating chlorinated sodium solid substance, obtains the nmp solution of sulphur lithium hydride; Continue at 150 ~ 190 DEG C to be heated to, without hydrogen sulfide effusion, obtain the NMP suspension of lithium sulfide; The lithium hydroxide of santochlor and catalytic amount is added in the ratio of lithium sulfide and santochlor mol ratio 0.95 ~ 1.1:1, carry out at 190 ~ 280 DEG C of temperature and 0.1 ~ 0.5MPa pressure condition and complete the polyreaction generating target product, collecting precipitation product after cooling.The fusing point of product 284 ~ 289 DEG C, weight-average molecular weight is 50000 ~ 52000, and molecular weight distributing index is 2 ~ 3, and chloride ion content is less than 300ppm.Owing to being removed by a large amount of sodium-chlor before polyreaction, solve the problem that the high and difficult removing of sodium chloride content in the product of traditional method causes product quality low.
Description
Technical field
The present invention relates to a kind of improvement to linear high molecular weight polyphenylene sulfide preparation method.
Background technology
Polyphenylene sulfide (PPS) i.e. polyphenylene sulfide, also known as poly-phenylene thioether, important chemical engineering plastics, it is the polyoxymethylene (POM) that continues, polycarbonate (PC), polymeric amide (PA), polybutylene terephthalate (PBT), with the sixth-largest engineering plastics after Noryl (MPPO), have excellent high temperature resistant, corrosion-resistant, radiation hardness, fire-retardant, balanced physical and mechanical properties and the feature such as fabulous dimensional stability and excellent electrical property, be widely used as structural macromolecular material, by filling, modifiedly be widely used as special engineering plastics, also can be made into various functional film, coating and matrix material, at electronic apparatus, aerospace, the fields such as Automobile Transportation succeed application.
The traditional method of industrial production of linear high molecular weight polyphenylene sulfide is that lithium chloride is catalyzer, at NMP(N-methyl-2-pyrrolidone with sodium sulphite and santochlor for main raw material) make the condition of solvent under obtain through high-temperature high-voltage reaction.The subject matter that the method exists, one is controllability and the poor reproducibility of technique, and unstable product quality, can only rely on subsequent analysis to classify; Two is the of poor quality of product, and molecular weight distribution is wide, is difficult to the requirement reaching the application of high demand; Three is that polyphenylene sulfide is in the course of the polymerization process to the inorganic salt impurities in 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 in polyphenylene sulfide product high, cause product seriously corroded to equipment in following process process; Four is that the feature of environmental protection of production technique does not pass a test, and produce a large amount of side product chlorinated sodium in production process and be difficult to refining, be difficult to after separation utilize, added value is low, low inferior to the recovery utilization rate of catalysts and solvents.Although US Patent No. 5235032 report a kind of with Sodium sulfhydrate and santochlor for raw material, NMP is solvent, with titanium reactor for the polyphenylene sulfide of low impurity content prepared by container, but its method not only cost is high, and the content of sodium ion is still higher, the degree of depth of still needing purifying.
Summary of the invention
For above-mentioned situation, the invention provides a kind of novel method preparing linear high molecular weight polyphenylene sulfide, can remove by sodium-chlor before polyreaction, solve the problems referred to above satisfactorily.
Before the present invention, desalination process prepares the method for linear high molecular weight polyphenylene sulfide, and be with N-Methyl pyrrolidone reaction medium, Sodium sulfhydrate and santochlor are the improvement that raw material carries out on polyreaction basis.Specifically carry out in the steps below:
1': at rare gas element, under being preferably conventional nitrogen environment protection, Sodium sulfhydrate being added and is dissolved with in the N-Methyl pyrrolidone of lithium chloride, under 70 ~ 110 DEG C of heating conditions after reaction, Isolating chlorinated sodium solid substance, obtains the N-Methyl pyrrolidone solution of sulphur lithium hydride;
2': by the N-Methyl pyrrolidone solution of above-mentioned sulphur lithium hydride, be heated to 150 ~ 190 DEG C under protection of inert gas, to without hydrogen sulfide effusion, obtains the N-Methyl pyrrolidone suspension of lithium sulfide;
3': N-Methyl pyrrolidone suspension santochlor raw material being added upper step lithium sulfide, under the existence of catalytic amount lithium hydroxide, carry out at 190 ~ 280 DEG C of temperature and 0.1 ~ 0.5MPa pressure condition and complete polyreaction, collecting precipitation product after cooling, obtains target product.Lithium sulfide wherein and the mol ratio of santochlor are 0.95 ~ 1.1:1.
Said protection of inert gas in above-mentioned preparation process, protects under being preferably conventional nitrogen environment.
On aforesaid method basis, the further preferred embodiment that can also adopt separately or in any combination comprises:
The temperature of reaction of said 1' step is preferably 75-95 DEG C.
The temperature of reaction of said 2' step is preferably 170 ~ 190 DEG C.
The said lithium sulfide of 3' step and the mol ratio of santochlor are preferably 0.95 ~ 1:1.
The polyreaction of said 3' step is under said pressure, preferably carry out in two steps: first under 0.1 ~ 0.2MPa pressure condition, carry out prepolymerization reaction 1 ~ 3 hour at 190 ~ 220 DEG C, then 220 ~ 280 DEG C are warming up to, continue to react 2 ~ 4 hours under 0.2 ~ 0.5MPa pressure condition, complete polyreaction.
When adopting said two-stage polymerization to react, the preferable reaction temperature that second step finally completes polyreaction is 250 ~ 280 DEG C.
For improving the crystallization yield of product further, one preferably, after said polyreaction completes, be cooled to≤120 DEG C after, add in reactant comprise the lesser tempss such as normal temperature (as 25 ~ 30 DEG C) water mixing, collect cooled precipitated product.。
In above-mentioned preparation method, after said 3' step polyreaction completes, to collected precipitated product, can be 60-80% with N-Methyl pyrrolidone part by weight respectively, after the aqueous solution being preferably 70% and water washing, dry, in order to removing as far as possible with reclaim catalyzer lithium hydroxide.By the detection to product fusing point, can check and judge the removal situation of impurity and the quality of product.Reaction solution after collecting precipitated product and the washing lotion of washed product, can merge aftertreatment, reclaims the compositions such as lithium chloride wherein and N-Methyl pyrrolidone, for reusing.
Experimental result shows, the above-mentioned linear polyphenylene sulfide product prepared of the present invention, and outward appearance is fine white powder, fusing point 284 ~ 289 DEG C, and weight-average molecular weight is 50,000 ~ 52, and 000, molecular weight distributing index is 2 ~ 3, and chloride ion content is less than 300ppm.Preparation method's circulation ratio that the present invention is above-mentioned and good stability.Due in the preparation process in accordance with the present invention, be actually lithium sulfide and santochlor carries out polycondensation, its feature and superiority are, lithium sulfide is on the one hand as reactive polymeric raw material, also there is corresponding self-catalysis simultaneously, under the lithium hydroxide auxiliary catalysis effect added further coordinates, be conducive to realizing and ensureing the high molecular of product and narrow molecular weight distribution.Because a large amount of sodium-chlor just removes by aforesaid method of the present invention before carrying out polyreaction, not only thoroughly solve the problem by sodium-chlor puzzlement in traditional method, but also greatly reduce the content of chlorion in product.Due at reaction conditions, be mainly derived from the chlorion of reaction raw materials santochlor, that the lithium chloride form be dissolved in completely in N-Methyl pyrrolidone exists, can not separate out, therefore the polyphenylene sulfide generated can not be enclosed with the lithium chloride of crystal form when separating out, lithium chloride can be removed (solubleness of lithium chloride in 25 DEG C of water is 67g, the 36g far above solubleness in the sodium-chlor generated in traditional method 25 DEG C of water) by washing accordingly, greatly improve the quality of product.
Embodiment is by the following examples 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 is only limitted to following example.Without departing from the idea case in the present invention described above, the various replacement made according to ordinary skill knowledge and customary means or change, all should comprise within the scope of the invention.
Accompanying drawing explanation
Fig. 1 is the Infrared spectroscopy figure of linear polyphenylene sulfide rosin products prepared by the inventive method.
Embodiment
embodiment 1
By abundant for the lithium chloride of 424g stirring and dissolving in the N-Methyl pyrrolidone of 3000g, the more abundant stirring suspension of the Sodium sulfhydrate adding 560g, in N
2under atmospheric condition, be slowly heated to 80 DEG C, react 3 hours, filter to obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride.The hot N-Methyl pyrrolidone of filter cake sodium-chlor 1000g 45 DEG C washs 3 times, obtains high pure white sodium chloride crystal 570g.
At N
2under atmospheric condition, the N-Methyl pyrrolidone solution of sulphur lithium hydride obtained above is heated to 150 DEG C, reacts and overflow without hydrogen sulfide to system, obtain the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas alkali liquor absorption.
735g santochlor and 36g lithium hydroxide is added in the N-Methyl pyrrolidone suspension of lithium sulfide obtained above, be warming up to 220 DEG C, self to be vaporized at such a temperature pressure (the i.e. pressure itself that produces by N-Methyl pyrrolidone in autoclave, be generally 0.1-0.2Mpa) prepolymerization 2 hours under condition, then 260 DEG C are warming up to, continue to react 3 hours under pressure itself (being generally 0.2 ~ 0.5MPa) condition, complete polyreaction.Reacting rear material is cooled to 120 DEG C, and the water " cold shock " adding 1500g room temperature is sized mixing, then lowers the temperature, crystalline deposit, filter, precipitated product 1500g 70%(w) N-Methyl pyrrolidone solution washing 3 times, distilled water wash 4 times, dry linear polyphenylene sulfide rosin products 478g, for fine white powder, fusing point 286 DEG C, weight-average molecular weight is 510000, molecular weight distributing index is 2.15, chloride ion content 291ppm.
By the KBr compressing tablet sample preparation of gained linear polyphenylene sulfide rosin products, be then placed in ThermoFisher Nicolet 6700 infrared spectrometer and scan, scanning resolution is 4 cm
-1, result as shown in Figure 1.Results of IR from Fig. 1: 1590cm
-1, 1470cm
-1, 1390cm
-1for the skeletal vibration absorption peak of phenyl ring, medium tenacity spike 1090cm
-1ar-S vibration on aromatic ring, 1905 cm
-1~ 1700 cm
-1several weak absorbing peaks are C-H out-of-plane vibration frequency multiplication and sum of fundamental frequencies peaks on Isosorbide-5-Nitrae-disubstituted benzenes ring, 818cm
-1strong absorption peak is C-H out-of-plane deformation vibration absorption peak on Isosorbide-5-Nitrae-disubstituted benzenes ring.This infrared spectrum and document (Li Wengang etc., " Infrared spectroscopy of thermal treatment polyphenylene sulfide ", analysis and test, 2012,35 (2): 71-73 etc.) infared spectrum of linear polyphenylene sulfide (PPS) resin reported is consistent, shows that this product is linear polyphenylene sulfide.
Filtrate after aforementioned " cold shock " sedimentation and filtration and 70%N-methyl-2-pyrrolidone aqueous solution washing lotion merge, and salt acid for adjusting pH to 8, distillation dewaters, and obtains the N-Methyl pyrrolidone solution 5952g of lithium chloride, can return sulphur lithium hydride preparation process and recycle.
embodiment 2
By abundant for the lithium chloride of 445g stirring and dissolving in the N-Methyl pyrrolidone of 4000g, the more abundant stirring suspension of the Sodium sulfhydrate adding 560g, in N
2under atmospheric condition, be slowly heated to 80 DEG C, react 3 hours, filter to obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride.The hot N-Methyl pyrrolidone of filter cake sodium-chlor 1500g 30 DEG C washs 2 times, obtains high pure white sodium chloride crystal 560g.
At N
2under atmospheric condition, the N-Methyl pyrrolidone solution of sulphur lithium hydride obtained above is heated to 190 DEG C, reacts and overflow without hydrogen sulfide to system, obtain the N-Methyl pyrrolidone suspension of lithium sulfide.Tail gas alkali liquor absorption.
By 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 DEG C of prepolymerizations 3 hours under pressure itself condition.Be warming up to 220 DEG C after reaction terminates, continue under pressure itself condition polyreaction 4 hours.After reaction terminates, be cooled to 120 DEG C, the water " cold shock " adding 2000g room temperature is sized mixing, lower the temperature, crystalline deposit, filters again, filter cake 2000g 70%N-methyl-2-pyrrolidone solution washing 2 times, distilled water wash 6 times, dry polyphenylene sulfide resin fat prod 465g, outward appearance is fine white powder, fusing point 284.5 DEG C, weight-average molecular weight is 50100, and molecular weight distributing index is 2.35, chloride ion content 295ppm.The filtrate obtained after previous reaction being terminated " cold shock " filtration and 70%N-methyl-2-pyrrolidone aqueous solution washing lotion merge, with salt acid for adjusting pH to 7, distillation dewaters, and obtains the N-Methyl pyrrolidone solution 6536g of lithium chloride, can be back to sulphur lithium hydride preparation process and recycle after composition adjustment.
embodiment 3
By abundant for the lithium chloride of 430g stirring and dissolving in the N-Methyl pyrrolidone of 5000g, the more abundant stirring suspension of the Sodium sulfhydrate adding 560g, in N
2slowly be heated to 80 DEG C under atmospheric condition, react 3 hours, filter to obtain the N-Methyl pyrrolidone solution of sulphur lithium hydride.The hot N-Methyl pyrrolidone of 1000g50 DEG C, filter cake sodium-chlor washs 3 times, obtains high pure white sodium chloride crystal 565g.
At N
2under atmospheric condition, the N-Methyl pyrrolidone solution of above-mentioned sulphur lithium hydride is heated to 170 DEG C, reacts without hydrogen sulfide effusion to system, the N-Methyl pyrrolidone suspension of obtained lithium sulfide.Tail gas alkali liquor absorption.
By 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 DEG C, prepolymerization 1 hour under pressure itself condition.Be warming up to 270 DEG C after reaction terminates, under pressure itself condition, continue reaction 2 hours, complete polyreaction.Be cooled to 120 DEG C after reaction terminates, the water " cold shock " adding 1500g room temperature is sized mixing, then lowers the temperature, crystalline deposit, filters.Filter cake 1500g 70%N-methyl-2-pyrrolidone solution washing 3 times, then use distilled water wash 6 times, dry, obtain linear polyphenylene sulfide product 470g, outward appearance is fine white powder, fusing point 289 DEG C, weight-average molecular weight is 514000, and molecular weight distributing index is 2.56, chloride ion content 285ppm.The filtrate obtained after previous reaction being terminated " cold shock " filtration and 70%N-methyl-2-pyrrolidone aqueous solution washing lotion merge, and salt acid for adjusting pH to 7.5, distillation dewaters, and obtains the N-Methyl pyrrolidone solution 7752g of lithium chloride.This solution can be back to sulphur lithium hydride preparation process and recycle after composition adjustment.
Claims (11)
1. before, desalination process prepares the method for linear high molecular weight polyphenylene sulfide, in N-Methyl pyrrolidone reaction medium, is prepared for raw material with Sodium sulfhydrate and santochlor through polyreaction, it is characterized in that carrying out in the steps below:
1': under protection of inert gas, adds Sodium sulfhydrate and is dissolved with in the N-Methyl pyrrolidone of lithium chloride, and under 70 ~ 110 DEG C of heating conditions after reaction, Isolating chlorinated sodium solid substance, obtains the N-Methyl pyrrolidone solution of sulphur lithium hydride;
2': by the N-Methyl pyrrolidone solution of above-mentioned sulphur lithium hydride, be heated to 150 ~ 190 DEG C under protection of inert gas, to without hydrogen sulfide effusion, obtains the N-Methyl pyrrolidone suspension of lithium sulfide;
3': N-Methyl pyrrolidone suspension santochlor raw material being added upper step lithium sulfide, under the existence of catalytic amount lithium hydroxide, carry out at 190 ~ 280 DEG C of temperature and 0.1 ~ 0.5MPa pressure condition and complete the polyreaction generating target product, collecting precipitation product after cooling, 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 that said 1' walks is 75-95 DEG C.
3. the method for claim 1, is characterized in that the temperature of reaction that said 2' walks is 170 ~ 190 DEG C.
4. the method for claim 1, is characterized in that the mol ratio of lithium sulfide and santochlor in the reaction of said 3' step is 0.95 ~ 1:1.
5. the method as described in one of Claims 1-4, is characterized in that the mol ratio of the lithium sulfide that said 3' walks and santochlor is 1
:1.
6. the method as described in one of Claims 1-4, it is characterized in that said 3' walks polyreaction and carries out in two steps under said pressure, first under 0.1 ~ 0.2MPa pressure condition, carry out prepolymerization reaction 1 ~ 3 hour at 190 ~ 220 DEG C, then 220 ~ 280 DEG C are warming up to, continue to react 2 ~ 4 hours under 0.2 ~ 0.5MPa pressure condition, complete polyreaction.
7. method as claimed in claim 6, is characterized in that the polyreaction of said second step is carried out at 250 ~ 280 DEG C of temperature.
8. the method as described in one of Claims 1-4, after it is characterized in that polyreaction that said 3' walks completes, be cooled to≤120 DEG C after, in reactant, add normal-temperature water mixing, collect cooled precipitated product.
9. the method as described in one of Claims 1-4, is characterized in that said 3' walks after the precipitated product collected is the aqueous solution of 60-80% and water washing with N-Methyl pyrrolidone part by weight respectively, 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 is 70%.
11. methods as described in one of Claims 1-4, is characterized in that 1' walks said protection of inert gas for conventional nitrogen protection.
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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 |
| 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 |
| CN106633062B (en) * | 2016-12-30 | 2018-12-28 | 浙江新和成特种材料有限公司 | A kind of polyphenylene sulfide of low chlorine content and preparation method thereof, resin combination and formed body |
| 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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| US5929203A (en) * | 1992-10-23 | 1999-07-27 | Phillips Petroleum Company | Process for preparing high molecular weight poly(arylene sulfide) polymers using lithium salts |
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| CN102482420A (en) * | 2009-08-27 | 2012-05-30 | 东丽株式会社 | Polyarylene sulfide and method for producing same |
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| US5929203A (en) * | 1992-10-23 | 1999-07-27 | Phillips Petroleum Company | Process for preparing high molecular weight poly(arylene sulfide) polymers using lithium salts |
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Effective date of registration: 20200108 Address after: 250204 Ji'nan, Zhangqiu, Shandong province Diao Zhen Chemical Industrial Park Patentee after: SHANDONG MINGHUA NEW MATERIAL CO., LTD. Address before: 610041, 1388, Tianfu Avenue, Chengdu hi tech Zone, Sichuan, USA, B766 Patentee before: Sichuan Baolifeng Chem Co., Ltd. |