阅读说明：本技术 一种聚苯硫醚与聚砜硫醚嵌段高聚物的合成方法 (Synthetic method of polyphenylene sulfide and polysulfone thioether block polymer ) 是由 杨伟明 张德明 周鸿文 于 2019-09-10 设计创作，主要内容包括：本发明所涉及的聚苯硫醚与聚砜硫醚嵌段高聚物的合成方法,采用三段式分别合成低聚物,最终得到是n个硫苯基团和m个硫砜基团的嵌段共聚物,合成方法是分段合成小分子低聚物,再由小分子低聚物扩链成高分子量的高聚物,且在反应合成时产生的NaCl先移出反应体系,使后面合成时,向有利于生成高聚物方向反应,该合成材料是在聚苯硫醚的基团引入了聚砜硫醚基团嵌段而成的高聚物,在315℃时的融指为100~300,热变形温度大于240℃,可进行拉膜处理；可溶解于部分强极性溶剂中,从而易于加工成膜。(The invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the steps of synthesizing oligomers in three stages respectively to finally obtain a block copolymer of n phenylene sulfide groups and m sulfone groups, wherein the synthesis method comprises the steps of synthesizing micromolecule oligomers in stages, then chain extending the micromolecule oligomers into high polymer with high molecular weight, removing NaCl generated in reaction synthesis firstly out of a reaction system, and enabling the NaCl generated in the later synthesis to react in the direction beneficial to the generation of the high polymer, the synthetic material is the high polymer formed by introducing polysulfone thioether group blocks into polyphenylene sulfide groups, the melt index is 100 ~ 300 at 315 ℃, the thermal deformation temperature is higher than 240 ℃, the film drawing treatment can be carried out, and the high polymer can be dissolved in a part of strong polar solvent, so that the film can be processed easily.)

1. A synthetic method of polyphenylene sulfide and polysulfone thioether block polymer comprises the following steps:

the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

Na2S·3H2O 300~360g；

n-methylpyrrolidine (NMP) 1500 ~ 6000 g;

putting the materials and the corresponding auxiliary agents into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

600 ~ 720g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using the nitrogen, starting heating for reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200 ~ 230 ℃, reacting for 3H, wherein the reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

Na2S·3H2O 450~550g；

1200 g of N-methylpyrrolidine (NMP) 1200 ~ 6000;

putting the materials and the corresponding auxiliary agents into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

p-Dichlorobenzene (DPCB) 530 ~ 650 g;

heating reaction, namely introducing nitrogen N2 into a reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using nitrogen N2, heating to 200 ~ 230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:

100 ~ 6900g of reaction solution A;

100 ~ 6900g of reaction solution B;

caprolactam 30 ~ 200 g;

LiCl 30~200g；

performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;

the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the air to P =0.1 ~ 2.0.0 mPa by using the nitrogen, closing the system, starting heating the reaction system, controlling the temperature to be 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;

and (3) heating the system to 230 ~ 245 ℃, reacting for 2H at constant temperature, heating to 250 ~ 265 ℃ for 2H, cooling to 100 ℃ after the reaction is finished, decompressing the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone sulfide block polymer.

2. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1, comprising the steps of:

the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

Na2S·3H2O 300~360g；

n-methylpyrrolidine (NMP) 1500 ~ 6000 g;

LiCl 20~40g；

sodium acetate 45 ~ 55 g;

NaOH 3~8 g；

putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, introducing nitrogen N2 into the reaction kettle, controlling the temperature to be 140 ℃ and ~ 200 ℃ and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

1000 ~ 3000g of N-methylpyrrolidine (NMP);

600 ~ 720g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using the nitrogen, starting heating for reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200 ~ 230 ℃, reacting for 3H, wherein the reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

Na2S·3H2O 450~550g；

1200 g of N-methylpyrrolidine (NMP) 1200 ~ 6000;

putting the materials and the corresponding auxiliary agents into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

p-Dichlorobenzene (DPCB) 530 ~ 650 g;

heating reaction, namely introducing nitrogen N2 into a reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using nitrogen N2, heating to 200 ~ 230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:

100 ~ 6900g of reaction solution A;

100 ~ 6900g of reaction solution B;

caprolactam 30 ~ 200 g;

LiCl 30~200g；

performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;

the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the air to P =0.1 ~ 2.0.0 mPa by using the nitrogen, closing the system, starting heating the reaction system, controlling the temperature to be 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;

and (3) heating the system to 230 ~ 245 ℃, reacting for 2H at constant temperature, heating to 250 ~ 265 ℃ for 2H, cooling to 100 ℃ after the reaction is finished, decompressing the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone sulfide block polymer.

3. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1, comprising the steps of:

the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

Na2S·3H2O 300~360g；

n-methylpyrrolidine (NMP) 1500 ~ 6000 g;

LiCl 20~40g；

sodium acetate 45 ~ 55 g;

NaOH 3~8 g；

putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, introducing nitrogen N2 into the reaction kettle, controlling the temperature to be 140 ℃ and ~ 200 ℃ and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

1000 ~ 3000g of N-methylpyrrolidine (NMP);

600 ~ 720g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using the nitrogen, starting heating for reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200 ~ 230 ℃, reacting for 3H, wherein the reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

Na2S·3H2O 450~550g；

1200 g of N-methylpyrrolidine (NMP) 1200 ~ 6000;

LiCl 40~60g；

NaOH 3~6g；

putting the materials into a reaction kettle, wherein LiCl and NaOH are used as auxiliary agents, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

100 ~ 2000g of N-methylpyrrolidine (NMP);

p-Dichlorobenzene (DPCB) 530 ~ 650 g;

heating reaction, namely introducing nitrogen N2 into a reaction kettle, pressurizing to P =0.1 ~ 2.0.0 mPa by using nitrogen N2, heating to 200 ~ 230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:

100 ~ 6900g of reaction solution A;

100 ~ 6900g of reaction solution B;

caprolactam 30 ~ 200 g;

LiCl 30~200g；

performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;

the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the air to P =0.1 ~ 2.0.0 mPa by using the nitrogen, closing the system, starting heating the reaction system, controlling the temperature to be 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;

and (3) heating the system to 230 ~ 245 ℃, reacting for 2H at constant temperature, heating to 250 ~ 265 ℃ for 2H, cooling to 100 ℃ after the reaction is finished, decompressing the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone sulfide block polymer.

4. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1, comprising the steps of:

the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

Na2S·3H2O 330g；

2200g of N-methylpyrrolidine (NMP);

LiCl 30g；

50g of sodium acetate;

NaOH 5 g；

putting the materials into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

1100g of N-methylpyrrolidine (NMP);

4, 4' -dichlorodiphenyl sulfone (DCDPS)660 g;

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing to P =0.3mPa by using the nitrogen, starting heating for reaction by a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 215-220 ℃ for reacting for 3H; the above reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

Na2S·3H2O 492g；

2000g of N-methylpyrrolidine (NMP);

LiCl 50g；

NaOH 5g；

putting the materials into a reaction kettle, introducing nitrogen N2 into the reaction kettle, controlling the temperature at 140 ℃ to ~ 200 ℃ and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

500g of N-methylpyrrolidine (NMP);

580g of p-Dichlorobenzene (DPCB);

heating for reaction: introducing nitrogen into the reaction kettle, pressurizing to P =0.30mPa by using the nitrogen, heating to 215-220 ℃ for reacting 2H, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

4000g of reaction liquid A;

3000g of a reaction solution B;

60g of caprolactam;

LiCl 80g；

performing dehydration reaction, introducing nitrogen, controlling the temperature at 140 ℃ and ~ 200 ℃ and dehydrating for 3H;

the first stage reaction, namely introducing nitrogen to replace the air in the reaction kettle, pressurizing the reaction kettle to P =0.30mPa by using the nitrogen, closing the system, starting heating the reaction kettle, controlling the temperature at 220 ~ 225 ℃, keeping the temperature for reaction for 2H, and pressurizing and pressing 10g of chain extension assistant under continuous stirring;

and (3) heating reaction in the second stage: and (3) heating the system to 240 ℃, reacting for 2H at constant temperature, heating to 250 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone thioether block polymer.

5. The method for synthesizing the polyphenylene sulfide and polysulfone sulfide block polymer as claimed in claim 1 ~ 4, wherein the reaction mixture is subjected to a post-reaction treatment by pouring the reaction mixture into 20kg of deionized water to precipitate a large amount of solid in the form of strands, washing, filtering, and drying.

6. The method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer according to claim 5, wherein the strip-shaped solid is crushed and then washed, and the washing process comprises: the solid is crushed and washed with deionized water for 7 times, and then washed with deionized water at high temperature of 130 ℃ under pressure for 2 times and filtered.

7. The method for synthesizing polyphenylene sulfide and polysulfone sulfide block polymer according to claim 6, wherein the solid powder obtained by washing and filtering is dried at 120 ℃ to obtain a dry solid powder having a moisture content of 0.35% or less.

8. The method for synthesizing the polyphenylene sulfide and polysulfone sulfide block polymer according to claim 1 ~ 4, wherein the chain extension assistant is trichlorobenzene, mononitrodichlorobenzene or dinitrochlorobenzene.

9. The method for synthesizing the polyphenylene sulfide and polysulfone thioether block polymer according to claim 4, wherein the synthesized material is a functional film material with very good toughness, has excellent electrical and mechanical properties, and can be used in the industries of electronics, automobiles, household appliances, aerospace and military industry.

[ technical field ] A method for producing a semiconductor device

The invention relates to the technical field of preparation of high molecular polymers, in particular to a preparation method of polyarylene sulfide sulfone.

[ background of the invention ]

The polyarylene sulfide sulfone (PASS) is an excellent engineering plastic, has good ductility, excellent mechanical and electrical properties, good dimensional stability, chemical corrosion resistance, radiation resistance, flame retardance and the like, and good film processability.

The polyphenylene sulfide and polysulfone sulfide block polymer is a chemical modified material which introduces sulfone groups on the basis of polyphenylene sulfide, and the introduction of polar sulfone groups enables the chemically modified polyphenylene sulfide new material to have a higher glass transition temperature which is as high as 180-220 ℃, so that the polyphenylene sulfide new material can be used for a long time in a higher temperature environment to keep the stability of physicochemical properties, can be dissolved in part of extremely strong solution, and has the properties which are not possessed by the original polyphenylene sulfide material. Therefore, compared with the polyphenylene sulfide material without modification, the polyphenylene sulfide and polysulfone sulfide block polymer after chemical modification is a material which is easier to process into a film.

Meanwhile, in some reactions for generating high polymers, a large amount of NaCl exists in the reaction solution and is always present in the reaction system, which is not favorable for the reaction in the direction of generating high polymers.

[ summary of the invention ]

The invention provides a chemically modified high polymer based on polyphenylene sulfide, and provides a synthetic method of a polyphenylene sulfide and polysulfone sulfide block high polymer, which has simpler preparation process and higher reaction efficiency.

The invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the following steps:

the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

Na₂S·3H₂O 300～360g；

1500-6000 g of N-methylpyrrolidine (NMP);

the materials and the corresponding auxiliary agents are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

600-720 g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, starting heating reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200-230 ℃ for reacting for 3H; the above reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

Na₂S·3H₂O 450～550g；

1200-6000 g of N-methylpyrrolidone (NMP);

the materials and the corresponding auxiliary agents are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

530-650 g of p-Dichlorobenzene (DPCB);

heating for reaction: introducing nitrogen N₂To the reaction kettle with nitrogen N₂Pressurizing until P is 0.1-2.0 mPa, heating to 200-230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:

performing dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 2-3H;

the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, sealing the system, starting heating reaction, controlling the temperature at 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring;

and (3) heating reaction in the second stage: heating the system to 230-245 ℃, reacting for 2H at constant temperature, heating to 250-265 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;

the molecular formula of the obtained high polymer of the polyphenylene sulfide sulfone and polysulfone sulfide block is as follows:

according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.

More particularly, the invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the following steps, wherein

The method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, and introducing nitrogen N into the reaction kettle₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

1000-3000 g of N-methylpyrrolidine (NMP);

600-720 g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, starting heating reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200-230 ℃ for reacting for 3H; the above reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

Na₂S·3H₂O 450～550g；

1200-6000 g of N-methylpyrrolidone (NMP);

the materials and the corresponding auxiliary agents are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

530-650 g of p-Dichlorobenzene (DPCB);

heating for reaction: introducing nitrogen N₂To the reaction kettle with nitrogen N₂Pressurizing until P is 0.1-2.0 mPa, heating to 200-230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:

performing dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 2-3H;

the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, sealing the system, starting heating reaction, controlling the temperature at 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring; the chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.

And (3) heating reaction in the second stage: heating the system to 230-245 ℃, reacting for 2H at constant temperature, heating to 250-265 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;

the molecular formula of the obtained high polymer of the polyphenylene sulfide sulfone and polysulfone sulfide block is as follows:

according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.

Still more particularly, the invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, comprising the following steps, wherein

The method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

putting the materials into a reaction kettle, wherein LiCl is used as a catalyst, sodium acetate and NaOH are used as auxiliaries, and introducing nitrogen N into the reaction kettle₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

1000-3000 g of N-methylpyrrolidine (NMP);

600-720 g of 4, 4' -dichlorodiphenyl sulfone (DCDPS);

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, starting heating reaction in a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 200-230 ℃ for reacting for 3H; the above reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

the materials are put into a reaction kettle, LiCl and NaOH are taken as auxiliary agents, and nitrogen N is introduced into the reaction kettle₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

100-2000 g of N-methylpyrrolidone (NMP);

530-650 g of p-Dichlorobenzene (DPCB);

heating for reaction: introducing nitrogen N₂To the reaction kettle with nitrogen N₂Pressurizing until P is 0.1-2.0 mPa, heating to 200-230 ℃ for 2H reaction, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

when the total amount of the reaction liquid A and the reaction liquid B is 7000g, the following components are mixed:

performing dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 2-3H;

the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.1-2.0 mPa, sealing the system, starting heating reaction, controlling the temperature at 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring; the chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.

And (3) heating reaction in the second stage: heating the system to 230-245 ℃, reacting for 2H at constant temperature, heating to 250-265 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;

the molecular formula of the obtained high polymer of the polyphenylene sulfide sulfone and polysulfone sulfide block is as follows:

according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.

More specifically, the synthesis method comprises the following steps:

the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

the above materials are put into a reaction kettle, wherein Na is contained in the materials₂S·3H₂O is used as main material, NMP provides reaction environment, NMP may be replaced by high boiling point ketone polar solvent such as cyclohexanone, 1, 3-dimethyl-2-imidazolidinone, etc., nitrogen N is introduced into the reactor after feeding₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

1100g of N-methylpyrrolidine (NMP);

4, 4' -dichlorodiphenyl sulfone (DCDPS)660 g;

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.3mPa, starting heating reaction by a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 215-220 ℃ for reacting for 3H; the above reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

the materials are put into a reaction kettle, LiCl and NaOH are taken as auxiliary agents, and nitrogen N is introduced into the reaction kettle₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

500g of N-methylpyrrolidine (NMP);

580g of p-Dichlorobenzene (DPCB);

heating for reaction: introducing nitrogen into the reaction kettle, pressurizing to 0.30mPa by using the nitrogen, heating to 215-220 ℃ for reacting for 2H, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

carrying out dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 3H;

the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing the reaction kettle to 0.30mPa by using the nitrogen, sealing the system, starting heating to react, controlling the temperature to be 220-225 ℃, and carrying out heat preservation reaction for 2H; 10g of chain extension assistant was pressed in under pressure with continuous stirring. The chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.

And (3) heating reaction in the second stage: and (3) heating the system to 240 ℃, reacting for 2H at constant temperature, heating to 250 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain the polyphenylene sulfide and polysulfone thioether block polymer.

The molecular formula of the obtained polyphenylene sulfide sulfone in the high polymer of the polysulfone sulfide block is as follows:

according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.

The molecular formula of the polyphenylene sulfide and polysulfone thioether block polymer obtained by the synthesis method is shown in the specificationStructurally, it isAndinstead of polysulfone sulfideBoth the structure and the polymerization mode are completely different. The chemical property, the mechanical property and the application scene of the high polymer modified material of polyphenylene sulfide synthesized by the invention are substantially different and greatly different from those of unmodified polyphenylene sulfide.

[ detailed description ] embodiments

The present invention will be described in further detail with reference to specific embodiments thereof.

The invention relates to a method for synthesizing polyphenylene sulfide and polysulfone thioether block polymer, which comprises the following steps:

the method comprises the following steps: in a 5L pressure autoclave, the following materials were charged:

the above materials are put into a reaction kettle, wherein Na is contained in the materials₂S·3H₂O is used as main material, NMP provides reaction environment, NMP may be replaced by high boiling point ketone polar solvent such as cyclohexanone, 1, 3-dimethyl-2-imidazolidinone, etc. after feeding, nitrogen N is introduced into the reactor₂Controlling the temperature at 140-200 ℃, and dehydrating for 3H;

step two: cooling to 120 ℃, and adding materials:

1100g of N-methylpyrrolidine (NMP);

4, 4' -dichlorodiphenyl sulfone (DCDPS)660 g;

heating for reaction, introducing nitrogen to replace air in the reaction kettle, pressurizing by using the nitrogen until P is 0.3mPa, starting heating reaction by a closed system, heating the system to 180 ℃, reacting for 2H at a constant temperature, and heating to 215-220 ℃ for reacting for 3H; the above reaction is exothermic;

step three: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering to remove salt while the solution is hot, obtaining polysulfone thioether oligomer at the moment, and taking reaction solution A for next synthesis;

step four: in a 5L reactor, the following materials were charged:

the materials are put into a reaction kettle, and nitrogen N is introduced into the reaction kettle₂Temperature ofControlling the temperature to be 140-200 ℃, and dehydrating for 3H;

step five: cooling to T less than or equal to 150 ℃, and adding materials:

500g of N-methylpyrrolidine (NMP);

580g of p-Dichlorobenzene (DPCB);

heating for reaction: introducing nitrogen into the reaction kettle, pressurizing to P & lt 0.3mPa by using the nitrogen, heating to 215-220 ℃ for reacting for 2H, carrying out exothermic reaction, and controlling the temperature;

step six: after the reaction is finished, cooling to 100 ℃, relieving the pressure of the system, and opening the kettle; filtering while the solution is hot to remove salt to obtain polyphenylene sulfide (PPS) oligomer reaction liquid B for next synthesis;

step seven: in a 10L pressure reactor, the following materials were charged:

carrying out dehydration reaction, introducing nitrogen, controlling the temperature at 140-200 ℃, and dehydrating for 3H;

the first stage reaction: introducing nitrogen to replace air in the reaction kettle, pressurizing the reaction kettle to 0.30mPa by using the nitrogen, sealing the system, starting heating to react, controlling the temperature to be 220-225 ℃, and carrying out heat preservation reaction for 2H; pressurizing and pressing 10g of chain extension auxiliary agent under continuous stirring; the chain extension auxiliary agent can be trichlorobenzene, mononitrodichlorobenzene, dinitrochlorobenzene and the like.

And (3) heating reaction in the second stage: heating the system to 240 ℃, reacting for 2H at constant temperature, heating to 250 ℃, reacting for 2H, cooling to 100 ℃ after the reaction is finished, relieving the pressure of the system, and opening the reaction kettle to obtain polyphenylene sulfide and polysulfone thioether block polymer;

the molecular formula of the obtained polyphenylene sulfide sulfone in the high polymer of the polysulfone sulfide block is as follows:

according to the above obtained product, post-reaction treatment was carried out: pouring the reaction solution into 20kg of deionized water, and separating out a large amount of strip-shaped solids; pulverizing the solid, washing with deionized water for 7 times, washing with deionized water at high temperature of 130 deg.C under pressure for 2 times, and filtering; drying the obtained solid powder at 120 deg.C to obtain dried solid powder with water content of below 0.35%.

We are a different material from the so-called polyarylene sulfide sulfone materials in other prior patent products because of the first: the structures of the prepared material and the prior polyarylene sulfide sulfone are completely different, and the structure isThe block copolymers of (A) are, as it were, those prepared by the so-called polyarylene sulfide sulfonesPolymer, second: the synthesis method comprises the steps of synthesizing small molecular oligomers in sections, and then chain extending the small molecular oligomers into high polymers with high molecular weight, so that the small molecular oligomers have application value, and the third step is as follows: NaCl (salt) produced during the synthesis of two-stage oligomer is first removed from the reaction system to react in the direction favorable to the formation of high polymer during subsequent synthesis

Preparing a high molecular weight poly (aryl sulfide sulfone) product in a specific mode, wherein the product contains m sulfosulfone groupsAnd n phenylene sulfide groupsThe block polymer of (1). Polysulfone thioether group block high polymer is introduced into polyphenylene sulfide groups, the block polymer is light gray to white powder, the melt index is 100-300 at 315 ℃, the thermal deformation temperature is more than 240 ℃, and film drawing treatment can be carried out. And because the polyphenylene sulfide group has polarity, the modified polyphenylene sulfide material can be dissolved in a part of strong polar solvent, so that the modified polyphenylene sulfide material is easy to process into a film.

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.