CN105283488A - Antistatic polyether sulfone composite material and preparation method therefor - Google Patents
Antistatic polyether sulfone composite material and preparation method therefor Download PDFInfo
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- CN105283488A CN105283488A CN201480030519.2A CN201480030519A CN105283488A CN 105283488 A CN105283488 A CN 105283488A CN 201480030519 A CN201480030519 A CN 201480030519A CN 105283488 A CN105283488 A CN 105283488A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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Abstract
Be related to a kind of polyether sulfone anti-static composite material and preparation method thereof, the molecular structure of the composite material such as formula (I): wherein (a) is carbon nanotube, and n is the degree of polymerization, value range 50-150. The composite material can be widely applied to electronic apparatus, pit mining, military industry field, and can provide different types of pellet and various sectional strips according to the market demand.
Description
Polyether sulfone anti-static composite material and preparation method thereof
Technical field belongs to polymeric material field the present invention relates to a kind of polyether sulfone anti-static composite material and preparation method thereof.Technical background polyethersulfone resin(PES) be ICI companies of Britain exploitation in 1972 a kind of excellent combination property thermoplastic macromolecule material, be one of special engineering plastics few in number for being applied.It has excellent heat resistance, physical and mechanical properties, fire resistance etc., particularly with can be used widely at high temperature continuously using and remain to the outstanding advantages such as retention property is stable in temperature environment jumpy in many fields.
But polyethersulfone resin is in application process, due to its electrical insulation property, material surface easily produces electrostatic, and this accumulation of static electricity is easily destroyed various devices and electronic product in application, it is particularly important especially in terms of mine safety, therefore it is very necessary to carry out antistatic treatment to it.The most frequently used method for preparing anti-static composite material at present is exactly by following process composite conducting material, for example, to be combined the CNT with excellent mechanical performance and electric property.But the inorganic conductive nano material including CNT has had a strong impact on its in the polymer dispersed due to its nano-scale, the double thin property in chemical inertness and surface, cause the excellent properties of CNT to be not in full use, therefore prepare the problem of Polymer/carbon Nanotubes Composites there are two cores:One is the dispersiveness for improving CNT in polymeric matrix;Two be to improve interfacial adhesion between CNT and polymer to act on.
To solve the two key problems, traditional method is modified to CNT progress surface and polyethersulfone resin carries out blending extrusion granulation.The shortcoming of this method is at 2 points, and one is due to that CNT belongs to inorganic material, and the double thin property in surface cause coupling agent to be difficult to play a role, and are acted on it is difficult to improve interfacial adhesion between CNT and polymer;Two be due to that specific surface area of carbon nanotube is big, is easily reunited, and causes bad dispersibility after its blending processing.The content of the invention present invention is for drawbacks described above there is provided a kind of polyether sulfone anti-static composite material, and gained composite has excellent electrical property and mechanical property.
The invention solves the problems that first technical problem a kind of polyether sulfone anti-static composite material is provided, its molecular structure is as follows:
Wherein ^ is CNT, and n is the degree of polymerization, and its span is 50 150.
The specific insulation of the polyether sulfone anti-static composite material is 107〜101()Ω cm, tensile strength is 100 130MPa, and elongation at break is 15 25%.
Further, the raw material of above-mentioned polyether sulfone anti-static composite material includes:DDS, 4,4- dihydroxydiphenylsulisomers, solvent, acyl chlorides carbon nano tube, dehydrating agent, catalyst;Feed molar is matched:DDS:4,4- dihydroxydiphenylsulisomers:Solvent:Dehydrating agent:Catalyst=1: 1: 5〜6: 1.3〜1.5:1, wherein, the consumption of acyl chlorides carbon nano tube is the 10 15% of DDS quality.
The solvent is sulfolane.
The dehydrating agent is toluene or benzene.
The catalyst is potassium hydroxide or sodium hydroxide.
Described acyl chlorides carbon nano tube is by made from following preparation processes:A, carboxylic carbon nano-tube preparation:CNT is subjected to the CNT that drying after acidification, washes clean obtains surface carboxyl groups in the nitration mixture that the concentrated sulfuric acid and concentrated nitric acid are constituted;B reacts the CNT of carboxylated the CNT for obtaining chloride under the catalytic action of dimethylformamide with thionyl chloride.
Further, the preparation process of the acyl chlorides carbon nano tube is:
1) acidification of CNT:The CNT for accounting for nitration mixture quality 2 5% is put into nitration mixture ultrasonic disperse 0.5-2 hours, diluted in 40-50 °C of reaction with deionized water after 20-30 hour, cleaning to pH value is washed with deionized water in gained sediment after suction filtration is 46, product is dried to obtain the CNT of surface carboxyl groups, wherein, nitration mixture is the mixture of the concentrated sulfuric acid and concentrated nitric acid, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3: 1;
2) CNT of carboxylated is added in thionyl chloride, dimethylformamide is added as catalyst, in 60-80 °C of heating reflux reaction 20-30 hours, reaction takes thionyl chloride out of after terminating using refluxing toluene, sealing preserve after lower floor's product drying is reclaimed, the CNT of chloride is obtained;Wherein, the mass ratio of CNT and thionyl chloride is 1:1000, the amount of dimethylformamide is the 1% of thionyl chloride quality.
Second technical problem to be solved by this invention is to provide the preparation side of above-mentioned polyether sulfone anti-static composite material
Method:CNT carries out chloride processing and obtains acyl chlorides carbon nano tube, gained acyl chlorides carbon nano tube again with DDS and 4,4- dihydroxydiphenylsulisomers carry out home position polymerization reaction, polyether sulfone anti-static composite material are obtained after drying;The home position polymerization reaction refers to:The CNT of chloride and 4,4- dichloro diphenyl sulfones and 4,4- dihydroxydiphenylsulisomers heating reflux reaction in the presence of catalyst, solvent and dehydrating agent, through crushing, washing and centrifugal dehydration after reaction product cooling, polyether sulfone anti-static composite material is produced after drying.
Further, in the preparation method of above-mentioned polyether sulfone anti-static composite material, the mol ratio of each raw material is DDS:4,4- dihydroxydiphenylsulisomers:Solvent:Dehydrating agent:Catalyst=1: 1: 5〜6: 1.3〜1.5: 1;The consumption of acyl chlorides carbon nano tube is the 10 15% of DDS quality.
Further, the preparation method of the polyether sulfone anti-static composite material:Comprise the steps:
(1) raw material is weighed according to the mol ratio of raw material:DDS:4,4- dihydroxydiphenylsulisomers:Solvent:Dehydrating agent:Catalyst=1: 1: 5〜6: 1.3- 1.5: 1;
(2) by acyl chlorides carbon nano tube, ultrasonic disperse is uniform in a solvent, again by 4,4- dichloro diphenyl sulfones, 4,4- dihydroxydiphenylsulisomers, solvent, acyl chlorides carbon nano tube, dehydrating agent, catalyst heating reflux reaction, wherein, the consumption of acyl chlorides carbon nano tube is the 10 15% of DDS quality;
(3) when temperature of charge is 120-160 °C, isothermal reaction 1-4 hours, it is further continued for being warming up to 170-210 °C of reaction to anhydrous generation, then dehydrating agent is all steamed, it is continuously heating to 2-4 hours blowings of 255-265 °C of reaction, crush, wash after products therefrom cooling, the centrifugal dehydration after solvent and catalyst are all removed is drying to obtain the polyether sulfone anti-static composite material of the present invention.
It is preferred that, in the step 3 of the above method, when temperature of charge is 120-160 °C, isothermal reaction 2 hours, is further continued for being warming up to 190 °C of reactions to anhydrous generation, then all steams dehydrating agent, it is continuously heating to 2-4 hours blowings of 255-265 °C of reaction, crushed after products therefrom cooling, wash paint, the centrifugal dehydration after solvent and catalyst are all removed is drying to obtain the polyether sulfone anti-static composite material of the present invention.
It is preferred that, the reaction of step 2 is carried out under nitrogen protection in methods described.
Beneficial effects of the present invention:The inventive method main advantage is that 2 points, one be solve CNT with the agglomeration traits in polyether sulfone recombination process, that is, disperse uneven;Two be that on the basis of the CNT of same amount, the antistatic property of Polyethersulfone Composites is better than the Polyethersulfone Composites prepared by prior art.Polyether sulfone anti-static composite material prepared by the present invention is in addition to possessing the excellent performance of special engineering plastics, also there is antistatic property, the fields such as electronic apparatus, pit mining, military project are can be widely applied to, and material can provide different types of pellet and various sectional strips according to the market demand.
Brief description of the drawings
Fig. 1 is polyether sulfone anti-static composite material section SEM photograph in the embodiment of the present invention 1.
Fig. 2 is the gained polyether sulfone anti-static composite material section SEM photograph of embodiment 2.Embodiment
The invention solves the problems that first technical problem a kind of polyether sulfone anti-static composite material is provided, its molecular structure is such as
Wherein ' be CNT, n is the degree of polymerization, its span be 50 150, n be more than 50 be in order to ensure that it reaches HMW, it is but also unsuitable too high, to ensure that polyether sulfone anti-static composite material possesses good processing characteristics.
The specific insulation of the polyether sulfone anti-static composite material is 107〜101()Ω cm, tensile strength is 100 130MPa, and elongation at break is 15 25%.
Further, the raw material of above-mentioned polyether sulfone anti-static composite material includes:DDS, 4,4- dihydroxydiphenylsulisomers, solvent, acyl chlorides carbon nano tube, dehydrating agent, catalyst;Its feed molar is matched:DDS:4,4- dihydroxydiphenylsulisomers:Solvent:Dehydrating agent:Catalyst=1: 1: 5〜6: 1.3〜1.5:1, wherein, the consumption of acyl chlorides carbon nano tube is the 10 15% of DDS quality.The consumption of acyl chlorides carbon nano tube is limited in the present invention as 4, the 10 15% of 4- dichloro diphenyl sulfone quality, chloride content of carbon nanotubes is unsuitable too high, otherwise can influence reaction, cause polyether sulfone molecular weight relatively low, it is too low, polyether sulfone antistatic property can be caused not good.
Described acyl chlorides carbon nano tube is by made from following preparation processes:A, carboxylic carbon nano-tube preparation:CNT is subjected to the CNT that drying after acidification, washes clean obtains surface carboxyl groups in the nitration mixture that the concentrated sulfuric acid and concentrated nitric acid are constituted;B reacts the CNT of carboxylated the CNT for obtaining chloride under the catalytic action of dimethylformamide with thionyl chloride.
Further, the preparation process of the acyl chlorides carbon nano tube is:
1) acidification of CNT:Will account for nitration mixture quality be 2 5% CNT be put into nitration mixture ultrasonic disperse 0.5-2 hours (;Preferably 1 hour is preferably 60 °C in 40-50 °C of C) reaction 20-30 hours (;Preferably 24 hours)
Diluted afterwards with deionized water, cleaning to pH value is washed with deionized water in gained sediment after suction filtration is 4-6 (being preferably 5), the CNT for obtaining surface carboxyl groups is dried and (be preferable in vacuum drying oven and dry) to product, wherein, nitration mixture is that volume ratio is 3:1 concentrated sulfuric acid and concentrated nitric acid is mixed;2) CNT of carboxylated is added in thionyl chloride, dimethylformamide is added as catalyst, in 60-80 °C of (being preferably 70 °C) heating reflux reaction 20-30 hours (being preferably 24 hours), reaction takes thionyl chloride out of after terminating using refluxing toluene, lower floor's product drying (being dried in vacuum drying oven) sealing preserve afterwards is reclaimed, the CNT of chloride is obtained;Its course of reaction equation is as shown below:
Second technical problem to be solved by this invention is to provide the preparation method of above-mentioned polyether sulfone anti-static composite material:CNT carries out chloride processing and obtains acyl chlorides carbon nano tube, gained acyl chlorides carbon nano tube again with DDS and 4,4- dihydroxydiphenylsulisomers carry out home position polymerization reaction, polyether sulfone anti-static composite material are obtained after drying;The home position polymerization reaction refers to:The CNT of chloride and DDS and 4,4- the dihydroxydiphenylsulisomer heating reflux reaction in the presence of catalyst, solvent and dehydrating agent, through crushing, washing and filter after reaction product cooling.
Further, in the preparation method of above-mentioned polyether sulfone anti-static composite material, the mol ratio of each raw material is DDS:4,4- dihydroxydiphenylsulisomers:Catalyst:Solvent:Dehydrating agent=1: 1: 1: 5〜6: 1.3〜1.5;The consumption of acyl chlorides carbon nano tube is the 10 15% of DDS quality.
Further, the preparation method of the polyether sulfone anti-static composite material:Comprise the steps:
(1) raw material is weighed according to the mol ratio of raw material:DDS:4,4- dihydroxydiphenylsulisomers:Potassium hydroxide:Sulfolane:Toluene=1: 1 : 1 : 5〜6: 1.3— 1.5;
(2) by acyl chlorides carbon nano tube, ultrasonic disperse is uniform in a solvent, again by 4,4- dichloro diphenyl sulfones, 4,4- dihydroxydiphenylsulisomers, solvent, acyl chlorides carbon nano tube, dehydrating agent, catalyst heating reflux reaction, wherein, the consumption of acyl chlorides carbon nano tube is the 10 15% of DDS quality;
(3) when temperature of charge is 120-160 °C, isothermal reaction 1-4 hours, it is further continued for being warming up to 170-210 °C of reaction to anhydrous generation, then dehydrating agent is all steamed, it is continuously heating to 2-4 hours blowings of 255-265 °C of reaction, crush, wash after products therefrom cooling, the centrifugal dehydration after solvent and catalyst are all removed is drying to obtain the polyether sulfone anti-static composite material of the present invention.
It is preferred that, in the step 3 of the above method, when temperature of charge is 120-160 °C, isothermal reaction 2 hours is further continued for being warming up to 190 °C of reactions to anhydrous generation, then all steams dehydrating agent, be continuously heating to 255-265 °C instead
Answering 2-4 hours, (polymerization time is generally 2-4 hours, mainly to ensure its molecular weight in zone of reasonableness))Blowing, crushes after products therefrom cooling, washs, the centrifugal dehydration after solvent and catalyst are all removed, and is drying to obtain the polyether sulfone anti-static composite material of the present invention.The synthetic reaction of polyether sulfone is divided into three sections in step 3 in the present invention, one is reaction generation oligomer, there is water generation during this, need to be taken it out with dehydrating agent, two be to need all to steam dehydrating agent, it is ensured that solvent good dissolubility, to ensure that reaction is normally carried out, three be polymerisation at high temperature, generates heavy polymer.
The present invention carries out chloride processing to antistatic additive carbon nano tube surface, and the CNT after chloride is dissolved in the polymerisation that polyethersulfone resin is directly participated in solvent, so as to realize polyether sulfone/CNT in-situ polymerization.
The method of the surface modification of carbon nanotube of abandoning tradition of the present invention, the polymerisation that polyethersulfone resin is directly participated in solvent is dissolved in carbon nano tube surface chloride relief CNT by Molecular Design, so as to realize polyether sulfone/CNT in-situ polymerization, the scattered and interface problem of CNT is thoroughly solved.
The present invention is specifically described below by embodiment; it is important to point out that embodiment is served only for further illustrating the present invention; it is not intended that limiting the scope of the invention, the those skilled in the art can make some nonessential modifications and adaptations according to the present invention.
The carbon nano tube surface chloride of embodiment 1 is handled
The first step is to carry out acidification to CNT:0.5g CNTs are put into 500ml nitration mixture(The concentrated sulfuric acid:Concentrated nitric acid volume ratio is 3:1) ultrasonic disperse 1 hour in, is diluted after 24 hours, cleaning to pH value is washed with deionized water in gained sediment after suction filtration is 5 or so, product dries the CNT for obtaining surface carboxyl groups in vacuum drying oven in 60 °C of reactions with deionized water(MWNT-COOH).Second step is that 0.2 gram of the CNT of carboxylated is added in 200ml thionyl chlorides, 2mlDMF is added as catalyst, in 70 °C of heating reflux reactions 24 hours, reaction takes thionyl chloride out of after terminating using refluxing toluene, sealing preserve after lower floor's product is dried in vacuum drying oven is reclaimed, the CNT (MWNT-COCl) of chloride is obtained.CNT SEM photograph after chloride is as shown in figure 1, as seen from Figure 1:There are a large amount of organic coating things in carbon nano tube surface, show that chloride method processing reaches ideal effect.
The preparation of the polyether sulfone anti-static composite material of embodiment 2
Following mol ratio is pressed first:DDS:4,4- dihydroxydiphenylsulisomers:Sulfolane:Toluene:Potassium hydroxide=1: 1: 5: 1.3:1 weighs raw material; weigh again and account for 4; ultrasonic disperse is carried out in the gained acyl chlorides carbon nano tube of the embodiment 1 input solvent sulfolane of 4- dichloro diphenyl sulfones quality 10% to handle 10 minutes; then by 4; 4- dichloro diphenyl sulfones, 4; 4- dihydroxydiphenylsulisomers, sulfolane, acyl chlorides carbon nano tube, toluene, potassium hydroxide are put into the reactor with reflux together, are stirred under nitrogen protection, heating.When temperature of charge is 155 °C, isothermal reaction 2 hours,
It is further continued for being warming up to 190 °C of reactions to anhydrous generation, then toluene is all steamed, blowing is diluted after being continuously heating to 255 reaction 2.5 hours.Material, which is put into cold water to take out after cooling, crushes centrifugation, and solid, which is put into 4 times of boiling water, to be washed five times, filters, and the polyether sulfone/carbon nanotube anti-static composite material for obtaining 200-500 mesh for 8 hours is then dried at 150 °C.Composite electrical property(25 °C of test temperature, humidity 70%) and mechanical property be shown in Table 1.Fig. 2 is gained composite section SEM photograph, and photo shows that CNT is uniformly dispersed in polyethersulfone resin matrix, and compatibility is fine.
Specific insulation is tested according to GB/T 15662-1995 in the embodiment of the present invention;Glass transition temperature is tested using the DSC instruments of TA companies of the U.S.;Tensile strength and elongation at break are tested according to GB/T1040.2.
The electrical property and mechanical property of polyether sulfone anti-static composite material prepared by the embodiment 2 of table 1
The preparation of the polyether sulfone anti-static composite material of embodiment 3
First raw material is weighed by following mol ratio:4 4- dichloro diphenyl sulfones:4 4- dihydroxydiphenylsulisomers:Sulfolane:Toluene:Potassium hydroxide=1: 1: 5: 1.3:1; weigh again in the acyl chlorides carbon nano tube input solvent sulfolane for account for 4 4- dichloro diphenyl sulfones quality 15% and carry out ultrasonic disperse processing 10 minutes; then 4 4- dichloro diphenyl sulfones, 4 4- dihydroxydiphenylsulisomers, sulfolane, CNT, toluene, potassium hydroxide are put into the reactor with reflux together; stir, heat under nitrogen protection.When temperature of charge is 155 °C, isothermal reaction 2 hours is further continued for being warming up to 190 °C of reactions to anhydrous generation, then all steams toluene, be continuously heating to 260 °C react 2.5 hours after dilute blowing.Material, which is put into cold water to take out after cooling, crushes centrifugation, and solid, which is put into 4 times of boiling water, to be washed five times, filters, and the polyether sulfone/carbon nanotube anti-static composite material for obtaining 200-500 mesh for 8 hours is then dried at 150 °C.Composite electrical property(25 °C of test temperature, humidity 70%) and mechanical property be shown in Table 2:
The electrical property and mechanical property of polyether sulfone anti-static composite material prepared by the embodiment 3 of table 2
Comparative example 1
Raw material proportioning and PROCESS FOR TREATMENT and all same of embodiment 2, the CNT differed only in comparative example 1 do not carry out chloride processing, then the electrical property and mechanical performance data of gained composite are as shown in table 3.
The electrical property and mechanical property of polyether sulfone anti-static composite material prepared by the comparative example 1 of table 3
As shown in Table 3, CNT handles the composite antistatic property finally given decline, and mechanical properties decrease without chloride under same process.
Claims (9)
- Claims1、Wherein ^ is CNT,nFor the degree of polymerization, its span be 50 15 (2nd, polyether sulfone anti-static composite material according to claim 1, it is characterised in that:The specific insulation of the polyether sulfone anti-static composite material is 107〜101()Ω cm, tensile strength is 100 130MPa, and elongation at break is 15 25%.3rd, polyether sulfone anti-static composite material according to claim 1 or 2, it is characterised in that:The raw material of the polyether sulfone anti-static composite material includes:DDS, 4,4- dihydroxydiphenylsulisomers, solvent, acyl chlorides carbon nano tube, dehydrating agent, catalyst;Feed molar is matched:DDS:4,4- dihydroxydiphenylsulisomers:Solvent:Dehydrating agent:Catalyst=1: 1: 5〜6: 1.3〜1.5 :1, wherein, the consumption of acyl chlorides carbon nano tube is the 10 15% of 4,4- dichloro diphenyl sulfone quality.4th, polyether sulfone anti-static composite material according to claim 3, it is characterised in that:The solvent is sulfolane.5th, polyether sulfone anti-static composite material according to claim 3, it is characterised in that:The dehydrating agent is toluene or benzene.6th, polyether sulfone anti-static composite material according to claim 3, it is characterised in that:The catalyst is potassium hydroxide or sodium hydroxide.7th, polyether sulfone anti-static composite material according to claim 3, it is characterised in that:Described acyl chlorides carbon nano tube is by made from following preparation processes:A, carboxylic carbon nano-tube preparation:CNT is subjected to the CNT that drying after acidification, washes clean obtains surface carboxyl groups in the nitration mixture that the concentrated sulfuric acid and concentrated nitric acid are constituted;The CNT of carboxylated is obtained acyl chlorides carbon nano tube by b under the catalytic action of dimethylformamide with thionyl chloride reaction.8th, the preparation method of the polyether sulfone anti-static composite material described in claim 1-7, it is characterised in that:CNT is first subjected to chloride processing and obtains acyl chlorides carbon nano tube, gained acyl chlorides carbon nano tube again with 4,4- dichloros Sulfone and 4,4- dihydroxydiphenylsulisomer carry out home position polymerization reaction, and polyether sulfone anti-static composite material is obtained after drying;The home position polymerization reaction refers to:The CNT of chloride and 4,4- dichloro diphenyl sulfones and 4,4- dihydroxydiphenylsulisomers heating reflux reaction in the presence of catalyst, solvent and dehydrating agent, through crushing, washing and centrifugal dehydration after reaction product cooling, is drying to obtain polyether sulfone anti-static composite material.9th, the preparation method of polyether sulfone anti-static composite material according to claim 8, it is characterised in that:First by acyl chlorides carbon nano tube, ultrasonic disperse is uniform in a solvent, then carries out home position polymerization reaction with DDS, 4,4- dihydroxydiphenylsulisomers.10th, the preparation method of polyether sulfone anti-static composite material according to claim 8 or claim 9, it is characterised in that:Heating reflux reaction is:When reaction temperature is 120-160 °C, isothermal reaction 1-4 hours is further continued for being warming up to 170-210 °C of reaction to anhydrous generation, then all steams dehydrating agent, be continuously heating to 255-265 °C and react 2-4 hours.11st, the preparation method of polyether sulfone anti-static composite material according to claim 8 or claim 9, it is characterised in that:The home position polymerization reaction is carried out under nitrogen protection.
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