CN115806670B - A combined post-treatment purification method for polyphenylene sulfide - Google Patents

A combined post-treatment purification method for polyphenylene sulfide Download PDF

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CN115806670B
CN115806670B CN202211535844.7A CN202211535844A CN115806670B CN 115806670 B CN115806670 B CN 115806670B CN 202211535844 A CN202211535844 A CN 202211535844A CN 115806670 B CN115806670 B CN 115806670B
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polyphenylene sulfide
sulfide resin
resin
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filter cake
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CN115806670A (en
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张跃
汪敏
马晓明
刘建武
严生虎
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Changzhou University
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Abstract

The invention belongs to the field of polyphenylene sulfide resin purification, and particularly provides a polyphenylene sulfide resin post-treatment purification method which comprises the steps of heating and suction filtering a crude product of the polyphenylene sulfide resin, washing and suction filtering with deionized water, drying a filter cake after washing, then putting the filter cake into a ball mill, adding an ethanol solution with the mass concentration of 60% -95%, grinding by zirconia beads with the particle size range of 0.6-1.8mm, separating out the resin, heating and stirring the resin with deionized water for multiple times, washing the resin while the resin is hot, suction filtering the resin, and drying the resin to obtain the high-purity polyphenylene sulfide resin.

Description

一种聚苯硫醚组合后处理纯化方法A combined post-treatment purification method for polyphenylene sulfide

技术领域Technical Field

本发明属于聚苯硫醚树脂纯化领域,具体涉及一种聚苯硫醚树脂后处理纯化方法。The invention belongs to the field of polyphenylene sulfide resin purification, and in particular relates to a polyphenylene sulfide resin post-processing purification method.

背景技术Background technique

聚苯硫醚(PPS)是聚芳硫醚中最重要、最常见的树脂品种之一。聚苯硫醚由于苯环结构的刚性和耐热性以及苯环和硫之间化学键的稳定性,赋予其分子高度稳定的化学键特性,具有优良的热稳定性、化学稳定性、尺寸稳定性以及电性能等。Polyphenylene sulfide (PPS) is one of the most important and common resins among polyarylene sulfides. Due to the rigidity and heat resistance of the benzene ring structure and the stability of the chemical bond between the benzene ring and sulfur, polyphenylene sulfide molecules are endowed with highly stable chemical bond characteristics, and have excellent thermal stability, chemical stability, dimensional stability and electrical properties.

在相关文献报道中,合成聚苯硫醚的反应路线有多种,但工业上主要采用硫化钠溶液缩聚法生产聚苯硫醚树脂。在聚苯硫醚树脂合成的过程中同时伴随着氯化钠的生成,另外还常常需要加入其它无机盐助剂,造成硫化钠和对二氯苯在溶剂体系下进行缩聚反应时,无机盐也会与产品同时溶解在有机溶剂中,最终得到的聚苯硫醚树脂中包裹着大量的无机盐、有机溶剂、低聚物等,这些杂质会影响树脂的力学性能、热稳定性、电绝缘性等性能,间接影响了聚苯硫醚树脂在国防军工、航空航天、电子封装元件等领域的应用。According to relevant literature reports, there are many reaction routes for synthesizing polyphenylene sulfide, but the sodium sulfide solution polycondensation method is mainly used in industry to produce polyphenylene sulfide resin. In the process of synthesizing polyphenylene sulfide resin, sodium chloride is also generated, and other inorganic salt additives are often added. When sodium sulfide and p-dichlorobenzene undergo polycondensation reaction in a solvent system, inorganic salts will also dissolve in the organic solvent at the same time as the product. The final polyphenylene sulfide resin is wrapped with a large amount of inorganic salts, organic solvents, oligomers, etc. These impurities will affect the mechanical properties, thermal stability, electrical insulation and other properties of the resin, and indirectly affect the application of polyphenylene sulfide resin in the fields of national defense, aerospace, electronic packaging components, etc.

专利CN112940255A公开了一种聚苯硫醚树脂的纯化处理工艺,采用硫化钠和对二氯苯为原料、N-甲基-2-吡咯烷酮为溶剂合成的聚苯硫醚树脂,对其进行过滤分离、分离出的滤饼中含有有机杂质,氯化钠、NMP溶剂、水分,洗涤干燥之后,再加入混合溶剂,将固-液体系的温度升至低于混合溶剂沸点,使聚苯硫醚树脂溶于混合溶剂之中,在保温一定时间后,加入去离子水,使聚苯硫醚结晶析出,经过固-液分离后,用低沸点溶剂萃取混合溶剂中的高沸点有机溶剂后,用去离子水洗涤聚苯硫醚树脂,可以得到高纯度的聚苯硫醚树脂。但是该方法操作繁琐,不适合工业生产。Patent CN112940255A discloses a purification process of polyphenylene sulfide resin, wherein the polyphenylene sulfide resin is synthesized by using sodium sulfide and p-dichlorobenzene as raw materials and N-methyl-2-pyrrolidone as solvent, filtering and separating the separated filter cake containing organic impurities, sodium chloride, NMP solvent, and water, washing and drying, adding a mixed solvent, raising the temperature of the solid-liquid system to below the boiling point of the mixed solvent, dissolving the polyphenylene sulfide resin in the mixed solvent, and adding deionized water after keeping the temperature for a certain period of time to crystallize the polyphenylene sulfide, and after solid-liquid separation, extracting the high boiling point organic solvent in the mixed solvent with a low boiling point solvent, and washing the polyphenylene sulfide resin with deionized water to obtain a high-purity polyphenylene sulfide resin. However, this method is cumbersome to operate and is not suitable for industrial production.

专利CN102731785A公开了一种聚苯硫醚的纯化方法,步骤如下:(1)酸碱中和:将聚合反应生成的聚苯硫醚树脂降温,加入酸,控制PH在3~4,搅拌下反应一段时间;(2)固液分离:将步骤(1)得到的反应产物降温并固液分离,得到聚苯硫醚固体;(3)溶剂洗涤:在(2)中得到的聚苯硫醚固体中加入有机溶剂,在搅拌状态下进行洗涤;(4)水蒸气蒸馏和水洗:将步骤(3)得到的聚苯硫醚在负压的条件下进行水蒸气蒸馏,并在蒸馏过程中回收残留于聚苯硫醚固体颗粒中的有机溶剂;当有机溶剂含量小于1%时,用75℃~85℃的蒸气冷凝水洗涤聚苯硫醚;(5)干燥包装:将步骤(4)得到的聚苯硫醚分离、干燥、包装。上述方法基于负压条件下进行水蒸气蒸馏,要求高,不适合工业生产。Patent CN102731785A discloses a method for purifying polyphenylene sulfide, and the steps are as follows: (1) acid-base neutralization: cool the polyphenylene sulfide resin generated by the polymerization reaction, add acid, control the pH to 3-4, and react for a period of time under stirring; (2) solid-liquid separation: cool the reaction product obtained in step (1) and separate the solid and liquid to obtain a polyphenylene sulfide solid; (3) solvent washing: add an organic solvent to the polyphenylene sulfide solid obtained in (2), and wash it under stirring; (4) steam distillation and water washing: steam distill the polyphenylene sulfide obtained in step (3) under negative pressure conditions, and recover the organic solvent remaining in the polyphenylene sulfide solid particles during the distillation process; when the organic solvent content is less than 1%, wash the polyphenylene sulfide with steam condensed water at 75°C to 85°C; (5) drying and packaging: separate, dry and package the polyphenylene sulfide obtained in step (4). The above method is based on steam distillation under negative pressure conditions, which has high requirements and is not suitable for industrial production.

发明内容Summary of the invention

为了尽可能去除聚苯硫醚树脂中包裹的杂质,得到高纯度的聚苯硫醚树脂,本发明提供一种聚苯硫醚树脂后处理纯化方法,具有简单高效的特点。In order to remove impurities contained in polyphenylene sulfide resin as much as possible and obtain high-purity polyphenylene sulfide resin, the present invention provides a polyphenylene sulfide resin post-treatment purification method, which has the characteristics of simplicity and high efficiency.

为了实现本发明目的,所采用的技术方案为:In order to achieve the purpose of the present invention, the technical solution adopted is:

一种聚苯硫醚树脂后处理纯化方法,包括如下步骤:A post-treatment purification method for polyphenylene sulfide resin comprises the following steps:

将聚苯硫醚树脂粗产物加热抽滤,去离子水洗涤抽滤(滤饼中含有溶剂及氯化钠等杂质,滤饼经过去离子水洗涤抽滤,可以去除树脂中部分杂质,但树脂内部还包裹着少量的氯化钠等杂质,这些在使用过程中会影响聚苯硫醚的性能),将洗涤后滤饼烘干然后放入球磨机中,并加入乙醇溶液,经不同粒径的氧化锆珠进行研磨,再分离出树脂,然后用去离子水加热搅拌多次洗涤并趁热抽滤,再烘干,得到高纯度的聚苯硫醚树脂。The crude polyphenylene sulfide resin product is heated and filtered, washed and filtered with deionized water (the filter cake contains impurities such as solvent and sodium chloride. The filter cake is washed and filtered with deionized water to remove some impurities in the resin, but a small amount of impurities such as sodium chloride are still wrapped inside the resin, which will affect the performance of polyphenylene sulfide during use), the washed filter cake is dried and then put into a ball mill, and ethanol solution is added, and it is ground with zirconium oxide beads of different particle sizes, and then the resin is separated, and then it is heated and stirred with deionized water for multiple washings and filtered while hot, and then dried to obtain high-purity polyphenylene sulfide resin.

加入乙醇溶液一起研磨,在研磨过程中有些杂质(部分盐和溶剂)随着快速旋转更易溶于乙醇溶液,这种情况下后续可用最少量的去离子水去除最大量的杂质。Add ethanol solution and grind together. During the grinding process, some impurities (part of the salt and the solvent) are more easily dissolved in the ethanol solution with rapid rotation. In this case, the maximum amount of impurities can be removed with the minimum amount of deionized water.

进一步的,聚苯硫醚树脂粗产物获得方法包括:,采用工业无水硫化钠和工业对二氯苯为原料、氯化锂为催化剂、N-甲基吡咯烷酮(NMP)为溶剂合成聚苯硫醚树脂,聚苯硫醚树脂分子量为4.2-4.8万。Furthermore, the method for obtaining the crude product of polyphenylene sulfide resin includes: using industrial anhydrous sodium sulfide and industrial p-dichlorobenzene as raw materials, lithium chloride as a catalyst, and N-methylpyrrolidone (NMP) as a solvent to synthesize polyphenylene sulfide resin, wherein the molecular weight of the polyphenylene sulfide resin is 42,000-48,000.

进一步的,聚苯硫醚树脂粗产物加热抽滤温度为80℃以上并维持10分钟以上再趁热进行抽滤,抽滤得到的固体,分离率能达到90%,即分离出90%以上的极性溶剂。Furthermore, the crude polyphenylene sulfide resin product is heated to a filtration temperature of 80° C. or higher and maintained for more than 10 minutes before filtration while hot. The solid obtained by filtration has a separation rate of 90%, that is, more than 90% of the polar solvent is separated.

进一步的,研磨后树脂加热搅拌多次洗涤次数为2-3次,加热温度为80℃以上并维持10分钟以上再趁热抽滤。Furthermore, the ground resin is heated and stirred for multiple washing for 2-3 times, the heating temperature is above 80° C. and maintained for more than 10 minutes before being filtered while hot.

进一步的,氧化锆球的粒径范围在0.6-12mm之间,研磨过程中可以更好促进乙醇溶液对杂质的溶出效果,优选粒径范围在0.6-1.8mm之间,滤饼装样量为球磨罐容积的50%-80%,优选装样量为球磨罐容积的66%。Furthermore, the particle size range of the zirconia balls is between 0.6-12 mm, which can better promote the dissolution effect of the ethanol solution on impurities during the grinding process. The preferred particle size range is between 0.6-1.8 mm. The filter cake loading amount is 50%-80% of the ball mill volume, and the preferred loading amount is 66% of the ball mill volume.

进一步的,研磨机器为制冷行星式球磨机,工作方式为四罐同时运转;制冷行星式球磨机的转速,公转范围为180-290r/min,优选公转为290r/min,自转范围为360-580r/min,优选自转为580r/min。Furthermore, the grinding machine is a refrigerated planetary ball mill, and the working mode is that four tanks run simultaneously; the speed of the refrigerated planetary ball mill has an orbital range of 180-290r/min, preferably an orbital range of 290r/min, and an autorotation range of 360-580r/min, preferably an autorotation range of 580r/min.

进一步的,乙醇溶液浓度在60%-95%,优选浓度范围是70%-95%。Furthermore, the concentration of the ethanol solution is between 60% and 95%, and preferably between 70% and 95%.

进一步的,烘干方法为在80~100℃条件下烘干8~10小时。Furthermore, the drying method is to dry at 80-100° C. for 8-10 hours.

本发明再对粗产物的趁热抽滤和加热洗涤抽滤的基础上,以研磨结合乙醇溶液溶出洗涤,实现氯离子和有机溶剂的有效去除,与现有技术相比,具有简单、高效的特点。The invention further combines grinding with ethanol solution dissolution and washing on the basis of hot filtration and heated washing filtration of the crude product to achieve effective removal of chloride ions and organic solvents. Compared with the prior art, the invention has the characteristics of simplicity and high efficiency.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为本发明实施例中聚苯硫醚制备和后处理的工艺流程图。FIG. 1 is a process flow chart of the preparation and post-treatment of polyphenylene sulfide in an embodiment of the present invention.

具体实施方式Detailed ways

下面通过实施例对本发明作进一步说明,但并不因此而限制本发明的内容和范围。The present invention will be further described below by way of examples, but the content and scope of the present invention are not limited thereby.

以下实施例和对比例中聚苯硫醚树脂的获得方法包括:,采用工业无水硫化钠和工业对二氯苯为原料、氯化锂为催化剂、N-甲基吡咯烷酮(NMP)为溶剂合成聚苯硫醚树脂,聚苯硫醚树脂分子量为4.2-4.8万。The method for obtaining the polyphenylene sulfide resin in the following examples and comparative examples includes: using industrial anhydrous sodium sulfide and industrial p-dichlorobenzene as raw materials, lithium chloride as a catalyst, and N-methylpyrrolidone (NMP) as a solvent to synthesize the polyphenylene sulfide resin, and the molecular weight of the polyphenylene sulfide resin is 42,000-48,000.

实施例1Example 1

(1)聚苯硫醚缩聚反应完成后,将聚苯硫醚树脂混合物加热到80℃以上并维持10分钟左右再趁热进行抽滤,抽滤得到的固体,分离率达到90%,即分离出90%以上的极性溶剂,滤饼固体待用,滤液回收;(1) After the polyphenylene sulfide polycondensation reaction is completed, the polyphenylene sulfide resin mixture is heated to above 80° C. and maintained for about 10 minutes and then filtered while hot. The solid obtained by filtration has a separation rate of 90%, that is, more than 90% of the polar solvent is separated. The filter cake solid is set aside and the filtrate is recovered;

(2)将(1)中的滤饼固体组分用去离子水搅拌洗涤,用水量为2L且需加热到80℃以上并维持10分钟左右再趁热进行抽滤,重复2-3次,滤饼固体烘干待用;(2) The solid components of the filter cake in (1) are washed with deionized water in an amount of 2 L and heated to above 80° C. and maintained for about 10 minutes, and then filtered while hot. This is repeated 2-3 times, and the filter cake solids are dried for later use;

(3)取出(2)中烘干的滤饼固体组分10克放进500ml球磨罐中,并加入浓度为95%乙醇溶液100mL,放入粒径为0.6-0.8mm的氧化锆球,总体装样量为球磨罐容积的66%,球磨机的转速设置为公转:290r/min,自转:580r/min,研磨10分钟后分离,分离的树脂待用;(3) Take out 10 g of the solid component of the filter cake dried in (2) and put it into a 500 ml ball mill, add 100 ml of 95% ethanol solution, put in zirconium oxide balls with a particle size of 0.6-0.8 mm, and the total sample volume is 66% of the volume of the ball mill. The speed of the ball mill is set to revolution: 290 r/min, rotation: 580 r/min, grind for 10 minutes and then separate, and the separated resin is set aside;

(4)将(3)中分离得到的树脂用去离子水加热搅拌,用水量为2L且需加热到80℃以上并维持10分钟左右再趁热抽滤,重复2-3次,滤饼固体待用,检测Cl-含量为0.01%;(4) The resin separated in (3) was heated and stirred with deionized water (2 L). The water amount was heated to above 80° C. and maintained for about 10 minutes. The resin was then filtered while hot. This process was repeated 2-3 times. The filter cake was set aside for use. The Cl- content was detected to be 0.01%.

(5)将(4)中的滤饼固体放入烘箱,在80~100℃条件下烘干8~10小时;(5) placing the filter cake solid in (4) into an oven and drying at 80-100° C. for 8-10 hours;

(6)称取一定量(5)中烘干后的聚苯硫醚树脂,放入马弗炉中焙烧,马弗炉温度设置:室温升至800℃,用时1小时,800℃保持8小时,800℃降至室温,用时3小时,然后将其取出,称量灰分的重量为0.08%。(6) Weigh a certain amount of the dried polyphenylene sulfide resin prepared in (5), and place it in a muffle furnace for calcination. The temperature of the muffle furnace is set as follows: from room temperature to 800° C. for 1 hour, maintained at 800° C. for 8 hours, and then reduced from 800° C. to room temperature for 3 hours. The resin is then taken out and the ash content is measured to be 0.08%.

实施例2Example 2

(1)聚苯硫醚缩聚反应完成后,将聚苯硫醚树脂混合物加热到80℃以上并维持10分钟左右再趁热进行抽滤,抽滤得到的固体,分离率达到90%,即分离出90%以上的极性溶剂,滤饼固体待用,滤液回收;(1) After the polyphenylene sulfide polycondensation reaction is completed, the polyphenylene sulfide resin mixture is heated to above 80° C. and maintained for about 10 minutes and then filtered while hot. The solid obtained by filtration has a separation rate of 90%, that is, more than 90% of the polar solvent is separated. The filter cake solid is set aside and the filtrate is recovered;

(2)将(1)中的滤饼固体组分用去离子水搅拌洗涤,用水量为2L且需加热到80℃以上并维持10分钟左右再趁热进行抽滤,重复2-3次,滤饼固体烘干待用;(2) The solid components of the filter cake in (1) are washed with deionized water in an amount of 2 L and heated to above 80° C. and maintained for about 10 minutes, and then filtered while hot. This is repeated 2-3 times, and the filter cake solids are dried for later use;

(3)取出(2)中烘干的滤饼固体组分10克放进500ml球磨罐中,并加入浓度为95%乙醇溶液100mL,放入粒径为0.8-1.0mm的氧化锆球,总体装样量为球磨罐容积的66%,球磨机的转速设置为公转:290r/min,自转:580r/min,研磨10分钟后分离,分离的树脂待用;(3) Take out 10 g of the solid component of the filter cake dried in (2) and put it into a 500 ml ball mill, add 100 ml of 95% ethanol solution, put in zirconium oxide balls with a particle size of 0.8-1.0 mm, and the total sample volume is 66% of the volume of the ball mill. The speed of the ball mill is set to revolution: 290 r/min, rotation: 580 r/min, grind for 10 minutes and then separate, and the separated resin is set aside;

(4)将(3)中分离得到的树脂用去离子水加热搅拌,用水量为2L且需加热到80℃以上并维持10分钟左右再趁热抽滤,重复2-3次,滤饼固体待用,检测Cl-含量为0.05%;(4) The resin separated in (3) was heated and stirred with deionized water (2 L). The water amount was heated to above 80° C. and maintained for about 10 minutes. Then, it was filtered while hot. This was repeated 2-3 times. The filter cake was set aside for use. The Cl- content was detected to be 0.05%;

(5)将(4)中的滤饼固体放入烘箱,在80~100℃条件下烘干8~10小时;(5) placing the filter cake solid in (4) into an oven and drying at 80-100° C. for 8-10 hours;

(6)称取一定量(5)中烘干后的聚苯硫醚树脂,放入马弗炉中焙烧,马弗炉温度设置:室温升至800℃,用时1小时,800℃保持8小时,800℃降至室温,用时3小时,然后将其取出,称量灰分的重量为0.12%。(6) Weigh a certain amount of the dried polyphenylene sulfide resin prepared in (5), and place it in a muffle furnace for calcination. The temperature of the muffle furnace is set as follows: from room temperature to 800° C. for 1 hour, maintained at 800° C. for 8 hours, and then reduced from 800° C. to room temperature for 3 hours. The resin is then taken out and the ash content is measured to be 0.12%.

实施例3Example 3

(1)聚苯硫醚缩聚反应完成后,将聚苯硫醚树脂混合物加热到80℃以上并维持10分钟左右再趁热进行抽滤,抽滤得到的固体,分离率达到90%,即分离出90%以上的极性溶剂,滤饼固体待用,滤液回收;(1) After the polyphenylene sulfide polycondensation reaction is completed, the polyphenylene sulfide resin mixture is heated to above 80° C. and maintained for about 10 minutes and then filtered while hot. The solid obtained by filtration has a separation rate of 90%, that is, more than 90% of the polar solvent is separated. The filter cake solid is set aside and the filtrate is recovered;

(2)将(1)中的滤饼固体组分用去离子水搅拌洗涤,用水量为2L且需加热到80℃以上并维持10分钟左右再趁热进行抽滤,重复2-3次,滤饼固体烘干待用;(2) The solid components of the filter cake in (1) are washed with deionized water in an amount of 2 L and heated to above 80° C. and maintained for about 10 minutes, and then filtered while hot. This is repeated 2-3 times, and the filter cake solids are dried for later use;

(3)取出(2)中烘干的滤饼固体组分10克放进500ml球磨罐中,并加入浓度为95%乙醇溶液100mL,放入粒径为1.0-1.2mm的氧化锆球,总体装样量为球磨罐容积的66%,球磨机的转速设置为公转:290r/min,自转:580r/min,研磨10分钟后分离,分离的树脂待用;(3) Take out 10 g of the solid component of the filter cake dried in (2) and put it into a 500 ml ball mill, add 100 ml of 95% ethanol solution, put in zirconium oxide balls with a particle size of 1.0-1.2 mm, and the total sample volume is 66% of the volume of the ball mill. The speed of the ball mill is set to revolution: 290 r/min, rotation: 580 r/min, grind for 10 minutes and then separate, and the separated resin is set aside;

(4)将(3)中分离得到的树脂用去离子水加热搅拌,用水量为2L且需加热到80℃以上并维持10分钟左右再趁热抽滤,重复2-3次,滤饼固体待用,检测Cl-含量为0.09%;(4) The resin separated in (3) was heated and stirred with deionized water (2 L). The water amount was heated to above 80° C. and maintained for about 10 minutes. The resin was then filtered while hot. This process was repeated 2-3 times. The filter cake was solid and set aside. The Cl- content was detected to be 0.09%.

(5)将(4)中的滤饼固体放入烘箱,在80~100℃条件下烘干8~10小时;(5) placing the filter cake solid in (4) into an oven and drying at 80-100° C. for 8-10 hours;

(6)称取一定量(5)中烘干后的聚苯硫醚树脂,放入马弗炉中焙烧,马弗炉温度设置:室温升至800℃,用时1小时,800℃保持8小时,800℃降至室温,用时3小时,然后将其取出,称量灰分的重量为0.16%。(6) Weigh a certain amount of the dried polyphenylene sulfide resin in (5), put it into a muffle furnace for calcination, and set the temperature of the muffle furnace: raise the temperature from room temperature to 800°C for 1 hour, maintain 800°C for 8 hours, and reduce the temperature from 800°C to room temperature for 3 hours. Then take it out and weigh the ash content, which is 0.16%.

实施例4Example 4

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

氧化锆球的粒径改为1.2-1.4mm;The particle size of zirconia balls was changed to 1.2-1.4mm;

根据此条件操作,Cl-检测含量为0.13%;灰分称量的重量为0.20%。According to this operating condition, the Cl- content is 0.13% and the ash weight is 0.20%.

实施例5Example 5

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

氧化锆球的粒径改为1.4-1.6mm;The particle size of zirconia balls was changed to 1.4-1.6mm;

根据此条件操作,Cl-检测含量为0.17%;灰分称量的重量为0.24%。According to this operating condition, the Cl- content was detected to be 0.17% and the ash content was weighed to be 0.24%.

实施例6Example 6

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

氧化锆球的粒径改为1.6-1.8mm;The particle size of zirconia balls was changed to 1.6-1.8mm;

根据此条件操作,Cl-检测含量为0.21%;灰分称量的重量为0.28%。According to this operating condition, the Cl- content was detected to be 0.21% and the ash content was weighed to be 0.28%.

实施例7Example 7

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇浓度改为90%;The ethanol concentration was changed to 90%;

根据此条件操作,Cl-检测含量为0.03%;灰分称量的重量为0.10%。According to this operating condition, the Cl- content is 0.03% and the ash weight is 0.10%.

实施例8Example 8

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇浓度改为85%;The ethanol concentration was changed to 85%;

根据此条件操作,Cl-检测含量为0.05%;灰分称量的重量为0.12%。According to this operating condition, the Cl- content is 0.05% and the ash weight is 0.12%.

实施例9Example 9

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇浓度改为80%;The ethanol concentration was changed to 80%;

根据此条件操作,Cl-检测含量为0.07%;灰分称量的重量为0.14%。According to this operating condition, the Cl- content was detected to be 0.07% and the ash content was weighed to be 0.14%.

实施例10Example 10

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇浓度改为75%;The ethanol concentration was changed to 75%;

根据此条件操作,Cl-检测含量为0.09%;灰分称量的重量为0.16%。According to this operating condition, the Cl- content was detected to be 0.09% and the ash content was weighed to be 0.16%.

实施例11Embodiment 11

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇浓度改为70%;The ethanol concentration was changed to 70%;

根据此条件操作,Cl-检测含量为0.11%;灰分称量的重量为0.18%。According to this operating condition, the Cl- content was detected to be 0.11% and the ash content was weighed to be 0.18%.

对比例1Comparative Example 1

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇溶液浓度改为50%;The concentration of ethanol solution was changed to 50%;

氧化锆球的粒径改为0.6-0.8mm;The particle size of zirconia balls was changed to 0.6-0.8mm;

根据此条件操作,Cl-检测含量为2.3%;灰分称量的重量为3.5%。Under this operating condition, the Cl- content was detected to be 2.3%; the ash content was weighed to be 3.5%.

对比例2Comparative Example 2

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇溶液浓度改为60%;The concentration of ethanol solution was changed to 60%;

氧化锆球的粒径改为0.8-1.0mm;The particle size of zirconia balls was changed to 0.8-1.0mm;

根据此条件操作,Cl-检测含量为2.5%;灰分称量的重量为3.8%。Under this operating condition, the Cl- content was detected to be 2.5%; the ash weight was weighed to be 3.8%.

对比例3Comparative Example 3

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇溶液浓度改为95%;The concentration of ethanol solution was changed to 95%;

氧化锆球的粒径改为2mm;The particle size of zirconia balls was changed to 2 mm;

根据此条件操作,Cl-检测含量为2.8%;灰分称量的重量为4.0%。Under this operating condition, the Cl- content was detected to be 2.8%; the ash content was weighed to be 4.0%.

对比例4Comparative Example 4

与实施例1的方法相同,区别在于:The method is the same as that of Example 1, except that:

乙醇溶液浓度改为90%;The concentration of ethanol solution was changed to 90%;

氧化锆球的粒径改为3mm;The particle size of zirconia balls was changed to 3mm;

根据此条件操作,Cl-检测含量为3.0%;灰分称量的重量为4.2%。According to this operating condition, the Cl- content was detected to be 3.0%; the ash content was weighed to be 4.2%.

对比例5Comparative Example 5

与实施例5的方法相同,区别在于:The method is the same as that of Example 5, except that:

球磨机的转速设置为公转:100r/min,自转:200r/minThe speed of the ball mill is set to revolution: 100r/min, rotation: 200r/min

根据此条件操作,Cl-检测含量为2.4%;灰分称量的重量为3.6%。Under this operating condition, the Cl- content was detected to be 2.4%; the ash weight was weighed to be 3.6%.

对比例6Comparative Example 6

与实施例6的方法相同,区别在于:The method is the same as that of Example 6, except that:

球磨机的转速设置为公转:50r/min,自转:100r/minThe speed of the ball mill is set to revolution: 50r/min, rotation: 100r/min

根据此条件操作,Cl-检测含量为2.9%;灰分称量的重量为4.1%。Under this operating condition, the Cl- content was detected to be 2.9%; the ash content was weighed to be 4.1%.

对比例7Comparative Example 7

聚苯硫醚树脂的处理过程及测试数据如表1所示:The processing and test data of polyphenylene sulfide resin are shown in Table 1:

(1)聚苯硫醚缩聚反应完成后,将聚苯硫醚树脂混合物加热到80℃以上并维持10分钟左右再趁热进行抽滤,抽滤得到的固体,分离率达到90%,即分离出90%以上的极性溶剂,滤饼固体待用,滤液回收;(1) After the polyphenylene sulfide polycondensation reaction is completed, the polyphenylene sulfide resin mixture is heated to above 80° C. and maintained for about 10 minutes and then filtered while hot. The solid obtained by filtration has a separation rate of 90%, that is, more than 90% of the polar solvent is separated. The filter cake solid is set aside and the filtrate is recovered;

(2)将(1)中的滤饼固体组分用去离子水搅拌洗涤,用水量为2L且需加热到80℃以上并维持10分钟左右再趁热进行抽滤,重复2-3次,滤饼固体待用,检测Cl-含量为3.8%;(2) The solid components of the filter cake in (1) were washed with deionized water in an amount of 2 L and heated to above 80° C. and maintained for about 10 minutes, and then filtered while hot. This was repeated 2-3 times. The filter cake solid components were set aside for use. The Cl- content was detected to be 3.8%;

(3)将(2)中的滤饼固体放入烘箱,在80~100℃条件下烘干8~10小时;(3) placing the filter cake solid in (2) into an oven and drying at 80-100° C. for 8-10 hours;

(4)称取一定量(3)中烘干后的聚苯硫醚树脂,放入马弗炉中焙烧,马弗炉温度设置:室温升至800℃,用时1小时,800℃保持8小时,800℃降至室温,用时3小时,然后将其取出,称量灰分的重量为5%。(4) Weigh a certain amount of the dried polyphenylene sulfide resin in (3), put it into a muffle furnace for calcination, and set the temperature of the muffle furnace: raise the temperature from room temperature to 800°C for 1 hour, maintain 800°C for 8 hours, and reduce the temperature from 800°C to room temperature for 3 hours. Then take it out and weigh the ash content, which is 5%.

表1Table 1

样品sample 灰分(%)Ash content (%) Cl-含量(%)Cl - content (%) 自制聚苯硫醚树脂Homemade polyphenylene sulfide resin 55 3.83.8

经本发明所述的后处理方法,可得到低盐低杂质的聚苯硫醚树脂,测试数据总结如下表2、表3所示:Through the post-treatment method of the present invention, a polyphenylene sulfide resin with low salt and low impurities can be obtained. The test data are summarized in Table 2 and Table 3 below:

表2Table 2

表3table 3

本发明纯化方法,可以提高聚苯硫醚的纯度,从而改善聚苯硫醚后续加工的性能。The purification method of the present invention can improve the purity of polyphenylene sulfide, thereby improving the performance of subsequent processing of polyphenylene sulfide.

以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical solutions and concepts of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims (6)

1. A polyphenylene sulfide resin post-treatment purification method is characterized in that: heating and suction-filtering a polyphenylene sulfide resin crude product, washing and suction-filtering with deionized water, drying a filter cake after washing, putting into a ball mill, adding an ethanol solution with the mass concentration of 70% -95%, grinding by zirconia beads with the particle size range of 0.6-1.8 mm, separating out resin, heating and stirring with deionized water for multiple times, washing and suction-filtering while hot, and drying to obtain high-purity polyphenylene sulfide resin;
the resin is heated, stirred and washed for a plurality of times for 2 to 3 times after grinding, the heating temperature is more than 80 ℃ and maintained for more than 10 minutes, and then the resin is filtered while the resin is hot;
the grinding machine is a refrigeration planetary ball mill, and the working mode is that four tanks are operated simultaneously; the revolution range is 180-290r/min, and the rotation range is 360-580 r/min.
2. The polyphenylene sulfide resin post-treatment purification method according to claim 1, wherein: the method for obtaining the polyphenylene sulfide resin crude product comprises the following steps: the industrial anhydrous sodium sulfide and industrial paradichlorobenzene are used as raw materials, lithium chloride is used as a catalyst, N-methylpyrrolidone is used as a solvent to synthesize the polyphenylene sulfide resin, and the molecular weight of the polyphenylene sulfide resin is 4.2-4.8 ten thousand.
3. The polyphenylene sulfide resin post-treatment purification method according to claim 1, wherein: the temperature of the heating and suction filtration of the polyphenylene sulfide resin crude product is more than 80 ℃ and maintained for more than 10 minutes, and then the suction filtration is carried out while the polyphenylene sulfide resin crude product is hot, and the separation rate of the solid obtained by the suction filtration reaches 90 percent.
4. The polyphenylene sulfide resin post-treatment purification method according to claim 1, wherein: the sample loading amount of the filter cake is 50% -80% of the volume of the ball milling tank.
5. The polyphenylene sulfide resin post-treatment purification method according to claim 1, wherein: the loading of the filter cake was 66% of the ball milling pot volume.
6. The polyphenylene sulfide resin post-treatment purification method according to claim 1, wherein: the drying method is that the drying is carried out for 8-10 hours at the temperature of 80-100 ℃.
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