CN102863621A - Polyphenylene sulfide resin refining method - Google Patents
Polyphenylene sulfide resin refining method Download PDFInfo
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- CN102863621A CN102863621A CN2012103593461A CN201210359346A CN102863621A CN 102863621 A CN102863621 A CN 102863621A CN 2012103593461 A CN2012103593461 A CN 2012103593461A CN 201210359346 A CN201210359346 A CN 201210359346A CN 102863621 A CN102863621 A CN 102863621A
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Abstract
The invention discloses a production method applicable to industrial refining of polyphenylene sulfide resin. The method includes the two steps of screening polyphenylene sulfide resin synthesis slurry and performing solvent washing for screened materials in the inert atmosphere. During solvent washing, the weight ratio of polyphenylene sulfide resin to solvent is 1:2-20, the washing operation temperature ranges from 100 DEG C to 220 DEG C, and the washing time ranges from 10 minutes to 300 minutes. By the method, the content of low polymers in the resin can be greatly lowered, the method and polyphenylene sulfide resin production can be carried out synchronously, the solvent is easy to recover, and produced polyphenylene sulfide resin can be used for producing fibers and films.
Description
Technical field
The present invention relates to a kind of process for purification of polyphenylene sulfide, particularly be applicable to a kind of process for purification that fibre-grade and film polyphenylene sulfide resin are produced.
Background technology
Polyphenylene sulfide (being called for short PPS) is a kind of high temperature resistant, corrosion resistant special engineering plastics, is widely used in the fields such as chemical, electronic apparatus, military project.Its main production method is sodium sulfide method, and this method, is carried out polycondensation and generated PPS in N-ethyl pyrrolidine ketone solvent take santochlor and sodium sulphite as main raw material under High Temperature High Pressure, synthetic slip after filtration, washing and drying obtain the PPS product.The PPS that this method is produced contains certain oligopolymer.
Chinese patent CN1597736A openly know clearly a kind of under normal pressure the purification process of PPS, do the purification process agent with polarity organic amide and tensio-active agent, under agitation heat to 180～250 ℃ and carry out purifying 2～8 h.Behind the purifying, cool to 60～80 ℃ of filtrations, filter cake is used first washing with acetone, and then washs with deionized water, and is dry after filtering, obtains highly purified PPS resin.Because the method need to use tensio-active agent to carry out smoothly when purification process, and the PPS after the purifying need to use acetone to wash, and process operations is complicated, and environmental pollution is large, and energy consumption is high.
Chinese patent CN1597736A discloses a kind of method that reclaims polyphenylene sulfide, and it repeatedly sieves by the p-poly-phenyl thioether, thereby obtains the finished product, but impurity wherein still can not fully be removed.
Guo Yue etc. are at its document (New Chemical Materials, 33(12), a kind of method of purifying polyphenylene sulfide is disclosed purification of PPS research), it sieves the PPS resin first, then wash with solvent, but its use is mixed solvent, solvent is difficult for reclaiming behind purifying, can not reuse, cost is higher, and is not suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of production method that can be applicable to industrial refining PPS is provided, this method can reduce the oligomer in the PPS resin greatly, the method can be carried out synchronously in conjunction with polyphenylene sulfide production, solvent is easy to reclaim, can directly reuse, the PPS of production can be used for making fiber and film.
In order to realize this purpose, present method comprises the steps:
(1): the slip screening
Because each component particles size differs larger in the PPS slip, wherein the PPS particle is more much bigger than all the other component particles, and investigator of the present invention finds can separate the oligopolymer in the slip with polyphenylene sulfide relatively easily by screening through research.
Method for sieving: will synthesize PPS resin slip and mix, then by 60-200 purpose screen filtrations, the undersize material that obtains being rich in the on-the-sieve material of polyphenylene sulfide particle and be dissolved with the polyphenylene sulfide oligopolymer, wherein undersize material is again by entering solvent recovering system behind the separating and filtering.
The temperature of screening operation slip preferably is controlled at 100～200 ℃, if temperature is crossed to hang down the polyphenylene sulfide oligopolymer that is dissolved in the solvent is separated out, and the too high boiling point that then may be higher than solvent causes solvent to be overflowed.Preferably 120～180 ℃ of more excellent service temperatures.
(2): the solvent wash operation
With polarity organic amide kind solvent, under inert atmosphere, under agitation heat in airtight band stirred vessel, the constant temperature appropriate time to be dissolving as far as possible oligopolymer at a certain temperature, thereby reduces oligomer in the resin.
Can use screening by the wet product of washing during solvent wash, or the on-the-sieve material after the screening is directly washed.
The organic amide kind solvent that the solvent wash operation can be adopted comprises N-Methyl pyrrolidone (referred to as NMP), N-ethyl pyrrolidone etc.Because what adopt during PPS is synthetic is that N-Methyl pyrrolidone is made solvent, in the solvent wash operation, preferably also use N-Methyl pyrrolidone to make solvent, be convenient to so follow-up solvent recuperation operation.
Solvent wash when operation the NMP that uses with the proportioning of PPS resin with resin dispersions of in solvent, try one's best, can stir and be advisable, if too little solvent then the abundant oligopolymer in the dissolving resin, if too much then the quantity of solvent of use is large, the cost height.Can be PPS weight: NMP weight=1:2～20, preferably 1:4～10.
For the air in the abundant delivery systme, need under inert atmosphere, carry out at normal temperatures first cold conditions and stir, then carry out gas displacement with rare gas element.Operable rare gas element comprises nitrogen, helium etc.
The oligopolymer that the service temperature in solvent wash when operation can be tried one's best in the dissolving resin with solvent is advisable.May cause resin generation crosslinking reaction if temperature is too high, cross to hang down and then can not fully dissolve oligopolymer.Suitable service temperature is 100～220 ℃, and better service temperature is preferably in 140～180 ℃.
The oligopolymer that the operating time in solvent wash when operation can try one's best in the dissolving resin with solvent is advisable.If overlong time then may cause resin generation crosslinking reaction, the time is too short then can not fully dissolve oligopolymer.The suitable operating time is 10～300 minutes, and better service temperature is preferably in 30～90 minutes.
Constant temperature cools to system after finishing, the terminal temperature of cooling is preferably in 80～150 ℃, be more preferably at 100～120 ℃, if excess Temperature then the slurry that may cause emitting occurs crosslinked in air, crossing the low then oligopolymer of dissolving may separate out, thereby be mixed in the resin, cause washing effect to reduce.
In order further to improve the solvent wash effect, can be behind the slurry filtration of emitting, with the organic amide solvent washing of heat once or repeatedly.Optional organic amide kind solvent comprises N-Methyl pyrrolidone, N-ethyl pyrrolidone etc.The temperature of hot solvent is preferably in 80～150 ℃, is more preferably at 100～120 ℃.
In order further to improve washing effect, the operation of this solvent wash can repeat more than twice or twice.
Embodiment
The present invention is further illustrated below by embodiment, but the present invention has more than and is limited to these examples.
Comparative example: get the synthetic slip of PPS, filter with link-suspended basket centrifuge, filter cake with deionized water normal temperature washing resin repeatedly, resin washs laggard row filtration and dry, obtain the PPS rosin products, measuring the product melt flow rate (MFR) is 232.15(g/10min), oligopolymer quality percentage composition is 3.12% in the product.
Embodiment 1: getting the slip with comparative example's same batch, is that the vibratory screening apparatus of 100 order Φ 1000 sieves filtration with screen cloth, and the on-the-sieve material after the screening is divided into identical two parts of weight, is labeled as respectively A and B.Get a on-the-sieve material (A) with deionized water wash repeatedly, resin washs laggard row filtration and dry, obtains PPS product (A), and measuring the product melt flow rate (MFR) is 221.86(g/10min).Oligopolymer quality percentage composition is 1.86% in the product.
Embodiment 2, get the on-the-sieve material (B) among the embodiment 1, carry out the solvent wash experiment.During washing (B) added the solvent wash still by the ratio of NMP and polyphenylene sulfide weight ratio 5:1, after becoming atmosphere of inert gases with nitrogen replacement, under airtight and stirring, is heated to 180 ℃, and under this temperature constant temperature 90 minutes.Then cool to 110 ℃, and filtered while hot, filter cake with deionized water wash repeatedly, resin washs that laggard row filters and be dry, obtains PPS product (B), measuring the product melt flow rate (MFR) is 202.86(g/10min).Oligopolymer quality percentage composition is 0.78% in the product.
Claims (6)
1. the process for purification of a polyphenylene sulfide, it comprises that the material that polyphenylene sulfide is synthesized after slip sieves and will sieve carries out two steps of solvent wash, polyphenylene sulfide weight during solvent wash: weight of solvent is 1:2-20, the washing operation temperature is 100-220 ℃, washing time is 10-300 minute, washing is carried out under inert atmosphere, and constant temperature cools to system after finishing, and the terminal temperature of cooling is 80～150 ℃.
2. polyphenylene sulfide process for purification according to claim 1 is characterized in that, the temperature of slip is 100-200 ℃ during screening.
3. polyphenylene sulfide process for purification according to claim 1 is characterized in that, the terminal temperature of cooling is 100～120 ℃.
4. polyphenylene sulfide process for purification according to claim 1, it is characterized in that, to synthesize PPS resin slip mixes, then by 60-200 purpose screen filtrations, the undersize material that obtains being rich in the on-the-sieve material of polyphenylene sulfide particle and be dissolved with the polyphenylene sulfide oligopolymer, wherein undersize material is again by entering solvent recovering system behind the separating and filtering.
5. polyphenylene sulfide process for purification according to claim 1 is characterized in that, used polyphenylene sulfide is that polyphenylene sulfide after the screening is directly used solvent wash during solvent wash, or screening is by the wet product of polyphenylene sulfide of washing.
6. polyphenylene sulfide process for purification according to claim 1 is characterized in that, described solvent is N-Methyl pyrrolidone.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012103593461A CN102863621A (en) | 2012-09-25 | 2012-09-25 | Polyphenylene sulfide resin refining method |
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| CN2012103593461A CN102863621A (en) | 2012-09-25 | 2012-09-25 | Polyphenylene sulfide resin refining method |
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| CN2012103593461A Pending CN102863621A (en) | 2012-09-25 | 2012-09-25 | Polyphenylene sulfide resin refining method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242529A (en) * | 2013-05-31 | 2013-08-14 | 常熟市金泉化纤织造有限责任公司 | Purifying refining method for high-molecular-weight polyphenylene sulfide |
| CN105601925A (en) * | 2016-01-19 | 2016-05-25 | 成都汇莹新材料有限公司 | Resin washing technique for production of polyphenylene sulfide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597736A (en) * | 2004-08-24 | 2005-03-23 | 四川大学 | Purification method of polyphenyl thioether |
| CN1896119A (en) * | 2005-07-13 | 2007-01-17 | 自贡鸿鹤化工股份有限公司 | Method for recovering polyphenyl resin from synthetic polyphenyl resin slurry |
| CN101010360A (en) * | 2004-09-06 | 2007-08-01 | 株式会社吴羽 | Process for producing polyarylene sulfide |
-
2012
- 2012-09-25 CN CN2012103593461A patent/CN102863621A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597736A (en) * | 2004-08-24 | 2005-03-23 | 四川大学 | Purification method of polyphenyl thioether |
| CN101010360A (en) * | 2004-09-06 | 2007-08-01 | 株式会社吴羽 | Process for producing polyarylene sulfide |
| CN1896119A (en) * | 2005-07-13 | 2007-01-17 | 自贡鸿鹤化工股份有限公司 | Method for recovering polyphenyl resin from synthetic polyphenyl resin slurry |
Non-Patent Citations (2)
| Title |
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| 《四川化工》 20101215 高艳等 "聚苯硫醚树脂纯化工艺研究" 第5页第2.2节 1-6 第13卷, 第6期 * |
| 高艳等: ""聚苯硫醚树脂纯化工艺研究"", 《四川化工》, vol. 13, no. 6, 15 December 2010 (2010-12-15) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242529A (en) * | 2013-05-31 | 2013-08-14 | 常熟市金泉化纤织造有限责任公司 | Purifying refining method for high-molecular-weight polyphenylene sulfide |
| CN105601925A (en) * | 2016-01-19 | 2016-05-25 | 成都汇莹新材料有限公司 | Resin washing technique for production of polyphenylene sulfide |
| CN105601925B (en) * | 2016-01-19 | 2018-01-16 | 成都汇莹新材料有限公司 | A kind of resin washing process technology in polyphenylene sulfide production |
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