阅读说明：本技术 一种制备高分子量聚芳硫醚砜的方法 (A method of preparing high molecular weight poly arylidene thio-ester sulfone ) 是由 张德明 于 2019-09-06 设计创作，主要内容包括：本发明是一种制备高分子量聚芳硫醚砜的方法,以含水硫化钠、4,4’-二氯二苯砜为原料,以氢氧化钠为助剂,以N-甲基吡咯烷酮为溶剂,以第三单体2,5-二硝基氯苯为扩链剂,并通过加入催化剂正丁基锂来提高分子量。本发明催化剂催化性能强,获得的聚芳硫醚砜分子量较高,产品质量比较稳定,采用水与聚乙二醇的混合液对聚芳硫醚砜树脂进行析出处理,效果好,产品颗粒均匀。(The present invention is a kind of method for preparing high molecular weight poly arylidene thio-ester sulfone, with aqueous vulcanized sodium, 4,4 '-dichloro diphenyl sulfones are raw material, using sodium hydroxide as auxiliary agent, using N-Methyl pyrrolidone as solvent, with Third monomer 2,5- dinitrofluorobenzene is chain extender, and improves molecular weight by the way that catalyst n-BuLi is added.Catalyst catalytic performance of the present invention is strong, and the polyaryl thioether sulfone molecular weight of acquisition is higher, and product quality is more stable, carries out precipitation processing to poly arylidene thio-ester sulphone resin using the mixed liquor of water and polyethylene glycol, effect is good, and product particle is uniform.)

1. a kind of method for preparing high molecular weight poly arylidene thio-ester sulfone, it is characterised in that: with aqueous vulcanized sodium, 4,4 '-dichloros Sulfone is raw material, and using sodium hydroxide as auxiliary agent, using N-Methyl pyrrolidone as solvent, with Third monomer 2,5- dichloronitrobenzene is to expand Chain agent, and molecular weight is improved by the way that catalyst n-BuLi is added, concrete technology flow process includes the following steps:

(1) prepolymerization: first load weighted N-Methyl pyrrolidone being added in polymeric kettle, opens stirring, then contains again by 3/4 Water vulcanized sodium, sodium hydroxide and by 4,4 '-dichloro diphenyl sulfones put into dehydrating kettle in, be passed through nitrogen protection；Temperature is increased to 140-200 DEG C, carry out aqueous vulcanized sodium dehydration；Prepolymerization occurs for vulcanized sodium and 4,4 '-dichloro diphenyl sulfones anti-during the dehydration process Prepolymer should be generated, is added dropwise after remaining 1/4 aqueous vulcanized sodium is diluted with 1-3 times of water in 180 DEG C, is dripped in dehydration Add, after being added dropwise, in 180 DEG C heat preservation 45-115 minutes, then rise to 200 DEG C, water smoking reaction terminates；

(2) it polymerize again: closed polymeric kettle, and logical nitrogen displaces air in polymeric kettle, raises the temperature to 205-235 DEG C, so Isothermal reaction 5-8h afterwards carries out polycondensation reaction, generates low-molecular weight polymer；

(3) chain extension: first by load weighted Third monomer 2,5- dinitrofluorobenzene is added in thinning tank, uses N-Methyl pyrrolidone It is diluted, obtains 2,5- dichloronitrobenzene dilution, 2,5- dichloronitrobenzene dilution and catalyst is slow by compression pump Slowly it is added dropwise in polymeric kettle；After being added dropwise, in 180-230 DEG C, continue isothermal reaction 1-4h；

(4) it is precipitated and separates: heavy polymer obtained in step (3) being cooled to 80-130 DEG C, discharging to receiver It is interior, then the heavy polymer that cooling obtains is slowly added in water and polyethylene glycol mixed liquor, obtains solidliquid mixture, Solidliquid mixture is separated through equipment for separating liquid from solid, obtains polyaryl thioether sulfone solid particle；

(5) polyaryl thioether sulfone solid particle obtained in step (4) is washed, dry, be packaged to be polyaryl thioether sulfone product.

2. according to the method described in claim 1, it is characterized by: the mass fraction for participating in each component of reaction is respectively as follows: and contains Water vulcanized sodium 1.0-1.1,4,4 '-dichloro diphenyl sulfone 1.0-1.1, catalyst 0.05-0.5, sodium hydroxide 0.05-0.4,2,5- bis- Chloronitrobenzene: 0.01-0.2, the catalyst are the benzole soln of 5% n-BuLi.

3. according to the method described in claim 2, it is characterized by: in the step (1) N-Methyl pyrrolidone additional amount Mass ratio with reactive component gross mass is (3-5): 1.

4. according to the method described in claim 2, it is characterized by: 2,5- dinitrofluorobenzene is diluted in the step (3) When, the volume ratio 1:(8-10 of 2, the 5- dinitrofluorobenzene and the N-Methyl pyrrolidone).

5. according to the method described in claim 3, it is characterized by: in step (4) water and polyethylene glycol mixed liquor, water and poly- Ethylene glycol ratio is 1:(2-8), the additional amount of water and polyethylene glycol is 4-9 times of the quality of heavy polymer.

6. according to the method described in claim 2, it is characterized by: the aqueous vulcanized sodium is five water vulcanized sodium.

Technical field

The invention belongs to novel high-performance thermoplastic resin fields, and in particular to a kind of to prepare high molecular weight poly arylidene thio-ester sulfone Method.

Background technique

Polyaryl thioether sulfone (PASS) is a kind of special engineering plastics of excellent combination property, not only maintains special engineered modeling Expect polyphenylene sulfide excellent heat-resisting, corrosion resistance and excellent mechanical property, and due to having in its molecular chain structure Aryl sulfone structure, so that this polymer has anti-impact, bending resistance, insulation and the mechanical behavior under high temperature more excellent than polyphenylene sulfide With radiation resistance, excellent processability and richer processing method and wider market, higher cost performance.Polyarylphosphorus Ether sulfone is prepared into the fabulous all kinds of corrosion-resistant seperation films of performance, is suitble to the functional film product of preparation high added value.

CN106832283B discloses a kind of method for preparing polyaryl thioether sulfone, with aqueous vulcanized sodium, 4,4 '-dichloros Sulfone is raw material, using sodium hydroxide as auxiliary agent, using N-Methyl pyrrolidone as solvent, using Third monomer as chain extender, and by adding Enter catalyst to improve molecular weight.Catalyst used in the technical solution is at least sodium acetate, lithium acetate, lithium chloride, benzene One kind of sodium sulfonate, sodium phosphate and sodium carbonate, catalytic capability are not to protrude very much, are difficult to obtain the poly arylidene thio-ester of high molecular weight Sulfone.Secondly, this method be precipitated and separating step used in be water, precipitation processing be not it is very good, which also deposits In many improvements.

In conclusion the application is in view of the deficiencies of the prior art, to provide a kind of preparation of high molecular weight poly arylidene thio-ester sulfone Method.

Summary of the invention

Object of the present invention is in view of the deficiencies of the prior art, with five water vulcanized sodium, 4,4 ' dichloro diphenyl sulfones for raw material, with hydrogen Sodium oxide molybdena is auxiliary agent, using N-Methyl pyrrolidone as solvent, with Third monomer: 2,5- dichloronitrobenzenes are chain extender, by rear Catalyst n-BuLi is added to improve molecular weight in phase, provides a kind of preparation method of high molecular weight poly arylidene thio-ester sulfone, can obtain Obtain the polyaryl thioether sulfone of stable product quality.It is described that technical scheme is as follows.

A method of high molecular weight poly arylidene thio-ester sulfone is prepared, with aqueous vulcanized sodium, 4,4 '-dichloro diphenyl sulfones are raw material, Using sodium hydroxide as auxiliary agent, using N-Methyl pyrrolidone as solvent, with Third monomer: 2,5- dichloronitrobenzenes are chain extender, and Molecular weight is improved by the way that catalyst n-BuLi is added, the concrete technology flow process of production includes the following steps:

(1) prepolymerization: first load weighted N-Methyl pyrrolidone being added in polymeric kettle, stirring is opened, then again by 3/4 Aqueous vulcanized sodium, sodium hydroxide and by 4,4 '-dichloro diphenyl sulfones put into dehydrating kettle in, be passed through nitrogen protection；By the system Temperature is increased to 140-200 DEG C, carries out aqueous vulcanized sodium dehydration；Vulcanized sodium and 4,4 '-dichloro diphenyl sulfones hair during the dehydration process Raw prepolymerization generates prepolymer, is added dropwise after remaining 1/4 aqueous vulcanized sodium is diluted with 1-3 times of water in 180 DEG C, side Side is dehydrated to be added dropwise, after being added dropwise, in 180 DEG C heat preservation 45-115 minutes, then rise to 200 DEG C, water smoking reaction terminates；

(2) it polymerize again: closed polymeric kettle, and logical nitrogen displaces air in polymeric kettle, which is increased to 205-235 DEG C, then isothermal reaction 5-8h, carries out polycondensation reaction, generates low-molecular weight polymer；

(3) chain extension: first by load weighted Third monomer 2,5- dinitrofluorobenzene is added in thinning tank, obtains after dilution 2,5- dinitrofluorobenzene dilutions 2,5- dichloronitrobenzene dilution and catalyst are slowly added dropwise to polymeric kettle by compression pump It is interior；After being added dropwise, in 180-230 DEG C, continue isothermal reaction 1-4h；Third monomer promotes low-molecular weight polymer at this stage Between continue polymerization reaction, ultimately generate heavy polymer；

(4) it is precipitated and separates: heavy polymer obtained in step (3) is cooled to 80-130 DEG C, discharging is to connecing It receives in device, then the heavy polymer that cooling obtains is slowly added in water and polyethylene glycol mixed liquor, it is mixed to obtain solid-liquid Close object.Solidliquid mixture is separated through equipment for separating liquid from solid, obtains polyaryl thioether sulfone solid particle；

(5) polyaryl thioether sulfone solid particle obtained in step (4) is washed, dry, be packaged to be polyaryl thioether sulfone Product.

The present invention uses 2,5- dichloronitrobenzene as chain extender, more living than the chain extenders such as trichloro-benzenes and paracide, aniline Property is strong.P2: the benzole soln containing 5% n-BuLi.The catalyst that other patents use is carboxylic acids, the sodium of benzoic acids, lithium Catalyst, and the n-BuLi that this patent uses is strong polymerization catalyst, can be improved polymerizable molecular amount.In prepolymerization Cheng Zhong rises to 200 DEG C of heat preservations 45-115 minutes, and it is more complete to be conducive to oligomer generation.Step (4) be added polyethylene glycol the purpose of be The organic matter being sticked on solid is removed, the higher product of purity can be obtained.

Preferably, the mass fraction for participating in each component of reaction is respectively as follows: aqueous vulcanized sodium 1.0-1.1,4,4 '-dichloros Diphenyl sulphone (DPS) 1.0-1.1, catalyst 0.05-0.5, sodium hydroxide 0.05-0.4,2,5- dichloronitrobenzene: 0.01-0.2.

Preferably, in the step (1) additional amount Yu reactive component gross mass of N-Methyl pyrrolidone mass ratio For (3-5): 1.

Preferably, when 2,5- dinitrofluorobenzene is diluted in the step (3), 2, the 5- dinitrofluorobenzene and institute State the volume ratio 1:(8-10 of N-Methyl pyrrolidone).

Preferably, in step (4) water and polyethylene glycol mixed liquor, the ratio of water and polyethylene glycol is 1:(2-8), water Additional amount with polyethylene glycol is 4-9 times of the quality of heavy polymer.

Preferably, the aqueous vulcanized sodium is five water vulcanized sodium.

The beneficial effects of the present invention are as follows:

(1) catalyst n-BuLi is added to improve molecular weight by the later period, using reasonable chain extension temperature, uses chain extension High molecular weight poly arylidene thio-ester sulphone resin is made in the method for polymerization；

(2) precipitation processing is carried out to poly arylidene thio-ester sulphone resin using the mixed liquor of water and polyethylene glycol, effect is good, product Grain is uniformly.

Specific embodiment

Specific embodiments of the present invention will be further explained below: