CN101139441A - Novel polysulfoneamide and acrylic terminated crosslinkable polysulfoneamide and preparation method thereof - Google Patents
Novel polysulfoneamide and acrylic terminated crosslinkable polysulfoneamide and preparation method thereof Download PDFInfo
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- CN101139441A CN101139441A CNA2007100561171A CN200710056117A CN101139441A CN 101139441 A CN101139441 A CN 101139441A CN A2007100561171 A CNA2007100561171 A CN A2007100561171A CN 200710056117 A CN200710056117 A CN 200710056117A CN 101139441 A CN101139441 A CN 101139441A
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Abstract
The present invention belongs to the field of macromolecule material, specifically relating to a novel type of polyphenylene sulfone and cross-linked polyphenylene sulfone high-performance material at the sealed end of propenylas well as the correspondent preparation methods of the two materials. Polyphenylene sulphone oligomer is firstly synthesized polyphenylene sulfone oligome is end-sealed by means of bifunctional monomer compound with propenyl structure under a certain condition. In this way, the cross-linkedpropenyl structure is introduced into the main structure of the polyphenylene sulphone material. The main structure of the polyphenylene sulphone material is end-sealed by means of propenyl so as to generate novel cross-linked polyphenylene sulphone high-performance material withpropenyl structure. Because the temperature for cross-linking action is relatively low (lower than 200 DEG C), the further improvement and enhancement on the performance of polyphenylene sulphone high-performance material withpropenyl sealed-end structure becomes practical. The present invention broadens the application range and the processing window of the material.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the end capped crosslinkable Polyphenylene Sulfone of a class novel polyphenyl sulfone polymer and propenyl, relate to the preparation method of the end capped crosslinkable Polyphenylene Sulfone of such Polyphenylene Sulfone and propenyl simultaneously.
Background technology
Polyphenylene Sulfone (PPSU) is the noncrystalline high performance thermoplastic engineering plastic of aromatic series that contains sulfuryl on the molecular backbone chain, has the flexibility of rigidity, thermotolerance and the polyarylether of polyarylsulphone concurrently.PPSU has unusual resistance to hydrolysis, high heat distortion temperature, extremely strong environmental stress crack resistance energy and excellent electric insulating energy.Dimensional stability is good, at room temperature has good deformation stability; Have outstanding thermostability, the life-time service temperature is 160 ℃, and the short-term use temperature is 190 ℃, can keep good performance in-100 ℃～+ 150 ℃ scopes.PPSU has excellent mechanical property, and tensile strength is 70～75MPa, modulus in flexure 2680MPa, and have outstanding long-term creep resistant, mechanical property still can remain unchanged in long-term time use.PPSU also has excellent dielectric properties, even be placed in the water or under 190 ℃ and still can keep very high dielectric properties, when descending long-time thermal ageing for 150 ℃, its physicals and electrical property change very little, and anti-steam performance is good, and its life-span was at least 12 years under 145 ℃ of steam, keeps the excellent electrical property performance simultaneously in wide temperature and range of frequency, its firing resistance satisfies stricter safety requirements, is the best kind of plastics aspect radiation resistance.PPSU is easy to machine-shaping, can reaches accurate tolerance, and is except that concentrated nitric acid, the vitriol oil, stable to chemical substances such as other acid, alkali, alcohol, aliphatic hydrocarbons.
The application of PPSU is very extensive, in electric field, PPSU can be used for making electric partss such as various contactors, connector, transformer insulated, silicon controlled rectifier cap, insulation thimble, coil rack, terminal stud and ring header, printed circuit board (PCB), axle sleeve, cover, TV systematic part, capacitor film, brushgear housing, Edison battery box etc.; At automobile, aviation field, PPSU can be used for making shield cap element, electric gear, battery cap, detonator, electronics firing mechanism element, lamp part, interior of aircraft accessory and aircraft exterior part, spacecraft exterior protection cover etc.Also can be used for PPSU and make luminaire plate washer, electric actuator, transmitter etc., be used for making the polysulfones-like polymer demand of cabin parts on the world market in the continuation growth, mainly be because the smog of the less calories that discharges during the burning of this base polymer, generation is few, the toxic gas diffusing capacity is few, meets the service requirements of security regulations fully; On kitchen tackle market, PPSU can replace glass and Stainless Steel Products to be used to make steam service plate, coffee vessel, cooking apparatus using microwave, milk and agricultural-food vessel, products such as egg cooker and milking apparatus parts, drink and food divider.PPSU is nontoxic goods, can be made into repeatedly the apparatus with Food Contact.PPSU is as transparent novel material, and heat-resisting water, stability to hydrolysis are better than other any thermoplasticss, so can be used for making coffee pot etc.Pipe connecting with PPSU makes is used for glass or glass enhanced polyester face, outer tube layer intensity height, and the inner tube layer chemicals-resistant, light than steel pipe, and transparent, be convenient to face control, be usually used in the oil lamp of foodstuffs industry and making strong light; Aspect health and medicine equipment, PPSU can be used for making surgical tray, atomizer, humidifier, contact lens anchor clamps, flow director, apparatus cover, dental appliance, fluid container, pacemaker, respiratory organ and laboratory apparatus etc.It is low than the glasswork cost that PPSU is used to make various medical articles, and be difficult for breaking, so can be used for tool housing, tooth section instrument, heart lobe box, blade cleaning system, the shaping box of soft contact lenses, microfilter, dialyzer etc.PPSU also can be used for having a denture made, and its bonding strength doubles than vinylformic acid; Aspect daily necessities, PPSU can be used for making humidifier, blower, clothes decatize, camera case, heat-resisting, hydrolysis products such as projector components and parts.Through the PPSU of 0.4-1.6MGy radiation and well dried mistake pellet, under 170 ℃ of 310 ℃ and mould temperature, be easy to injection moulding, be applicable to the tackiness agent of laminating material, polysulfones such as PPSU-SR, the PKXR etc. of all band silane all can be used as tackiness agent, be used for starching glass and graphite fibre and make matrix material, PPSU with graphite cloth enhanced band silylation can make aircraft componentss such as elevating rudder.PPSU can increase wear resistance and physical and mechanical properties after adding the solid lubricant tetrafluoroethylene, also be applied to prepare wear resistnat paint; In addition, PPSU also can make various chemical industry processing unitss (as pump outer cover, tower external protection etc.), food processing plant, pollution control equipment, milk preparation processing units and engineering, building, chemical industry with pipeline etc.
The PPSU exploitation prospect is wide, and PPSU is mainly used in electronics, electric aspect at present.Electronics, electricly develop, promoted the growth of PPSU consumption to small-sized, light weight, high temperature resistant direction.At automobile, the demand of PPSU is still in the impetus that keeps steady growth in space flight, medical treatment, the health.
Summary of the invention
One of purpose of the present invention provides a kind of Polyphenylene Sulfone polymkeric substance of brand new;
Two of purpose of the present invention provides a kind of preparation method of Polyphenylene Sulfone polymkeric substance;
Three of purpose of the present invention provides the end capped crosslinkable Polyphenylene Sulfone of a kind of propenyl;
Four of purpose of the present invention provides the preparation method of the end capped crosslinkable Polyphenylene Sulfone of a kind of propenyl.
The present invention is preparation novel polyphenyl sulfone polymer material and the end capped Polyphenylene Sulfone series material of propenyl, utilize the propenyl end group (to be lower than 200 ℃) at a lower temperature crosslinking reaction can take place, form the characteristics of cross-linked structure, can further improve the use temperature of this type of material, successfully prepare crosslinkable novel polyphenyl sulfone high performance material.Have great practical value and develop value for the high performance of polyarylsulphone class material, thereby reach the purpose that the performance that makes propenyl end capped crosslinkable Polyphenylene Sulfone material and crosslinked back Polyphenylene Sulfone material can satisfy different use temperatures and use range.
The reaction process of high new texture Polyphenylene Sulfone (PPSU) polymkeric substance is: under the room temperature be with mol ratio 1～1.03: 14,4 '-difluoro benzophenone or 4,4 '-difluoro triphen diketone and 4,4 '-dihydroxy diphenylsulphone joins in organic solvent sulfobenzide or the tetramethylene sulfone, solid content in the reaction system is 20%～35%, behind the heating and melting, add molar weight with respect to 4, the salt of wormwood of 4 '-dihydroxy diphenylsulphone excessive 3～5% is made catalyzer; Stirring heats up and carries out repeatedly getting polymer product after the temperature control reaction, with polymer product discharging in cold water, thick product is pulverized through pulverizer, the powdered sample that obtains with ethanol or washing with acetone repeatedly to remove organic solvent, then with the distilled water boiling washing repeatedly to remove inorganic salt, final product obtains white Polyphenylene Sulfone polymer powder sample at 110～120 ℃ of drying 10～15h, and productive rate is 96～98%;
Repeatedly temperature control reaction described in the top method, be meant in stirring temperature-rise period, constant or in very little scope, change at a certain temperature place control temperature of reaction system, carry out the reaction of certain hour then, make the temperature rapid (5～10 minutes) of reaction system be increased to temperature of reaction next time after question response finishes again;
Further, repeatedly temperature control reaction described in the top method is to carry out 2～5 times temperature control reaction in 200～320 ℃ of temperature ranges, the temperature interval of per twice temperature control reaction is 10～50 ℃, and the time of each temperature control reaction is 1～5 hour, and the temperature control scope of each temperature control reaction is 5～10 ℃;
Further, above the repeatedly temperature control reaction described in the method be in 230～240 ℃, 250～260 ℃, 280～290 ℃ temperature ranges, to react respectively 1～3 hour, at 310～320 ℃ of temperature range internal reaction 3～5h.
The Polyphenylene Sulfone polymer architecture formula following (corresponding embodiment 1,2) of this patent preparation:
(I) n represents the polymerization degree, for greater than 1 positive integer
Corresponding embodiment 3,4:
(II) n is the positive integer greater than 1
Synthesizing of the end capped crosslinkable Polyphenylene Sulfone of propenyl: will carry out end-blocking with the bifunctional monomer's compound p-poly-phenyl sulfone oligopolymer that contains the propenyl structure under certain condition by nucleophilic substitution route synthetic Polyphenylene Sulfone oligopolymer, thereby crosslinkable propenyl structure is incorporated in the backbone structure of Polyphenylene Sulfone material.
Specifically, the first step be at room temperature be with mol ratio 1.05～1.15: 14,4 '-difluoro benzophenone or 4,4 '-difluoro triphen diketone and 4,4 '-dihydroxy diphenylsulphone joins in the organic solvent, and solid content is 20%～30%, behind the heating and melting, add molar weight with respect to 4, the salt of wormwood catalyzer of 4 '-dihydroxy diphenylsulphone excessive 3～5%; After stirring intensification and carrying out repeatedly the temperature control reaction, with the discharging in cold water of gained Polyphenylene Sulfone oligopolymer, thick product is pulverized through pulverizer, the powdered sample that obtains with ethanol or washing with acetone to remove organic solvent, then with the distilled water boiling washing to remove inorganic salt, final product obtains white Polyphenylene Sulfone oligopolymer powdered sample at 110～120 ℃ of drying 10～15h, and productive rate is 96-98%.With preparation Polyphenylene Sulfone polymer phase ratio, because the difference of raw material amount ratio, cause the n value among structural formula (III), (IV) and structural formula (I), (II) that very big difference is arranged, the n value of structural formula (III), (IV) is little more a lot of than structural formula (I), (II), and promptly the molecular weight of the molecular weight ratio Polyphenylene Sulfone polymkeric substance of Polyphenylene Sulfone oligopolymer is little a lot.
Second step was under room temperature the Polyphenylene Sulfone oligopolymer to be joined in the organic solvent, solid content is 20%～30%, after the heating for dissolving, adding molar weight is the bifunctional monomer's compound 2 that contains the propenyl structure of 1.03～1.05 times of Polyphenylene Sulfone oligopolymers, 2 '-diallyl dihydroxyphenyl propane, its objective is 2,2 '-diallyl dihydroxyphenyl propane is excessive, guarantees that the oligopolymer end group is by its end-blocking; Add molar weight again with respect to 2, the salt of wormwood catalyzer of 2 '-diallyl dihydroxyphenyl propane excessive 3～5% its objective is to guarantee 2, whole salifies in 2 '-diallyl dihydroxyphenyl propane end-blocking process.After stirring intensification and carrying out repeatedly the temperature control reaction, with products obtained therefrom discharging in cold water, thick product is pulverized through pulverizer, the powdered sample that obtains with ethanol or washing with acetone to remove organic solvent, then with the distilled water boiling washing to remove inorganic salt, final product obtains the end capped crosslinkable Polyphenylene Sulfone of white propenyl powdered sample at 110～120 ℃ of drying 10～15h, and productive rate is 96-98%.
In the top method, the organic solvent that preparation Polyphenylene Sulfone oligopolymer uses is a sulfobenzide, and the organic solvent that the end capped crosslinkable Polyphenylene Sulfone of preparation propenyl is used is N-Methyl pyrrolidone or tetramethylene sulfone.
Further, in the aforesaid method when preparation Polyphenylene Sulfone oligopolymer, described repeatedly temperature control reaction is to carry out 2～5 temperature control reactions in 200～320 ℃ of temperature ranges, per twice temperature control temperature of reaction is spaced apart 10～50 ℃, each temperature control reaction 1～5 hour, the temperature range of each temperature control reaction is 5～10 ℃; When the end capped crosslinkable Polyphenylene Sulfone of preparation propenyl, described repeatedly temperature control reaction is to carry out 2～3 temperature control reactions in 140～180 ℃ of temperature ranges, per twice temperature control temperature of reaction is spaced apart 10～20 ℃, each temperature control reaction 1～3 hour, the temperature range of each temperature control reaction is 5～10 ℃;
Further, when preparation Polyphenylene Sulfone oligopolymer, described repeatedly temperature control reaction is to react respectively 1～5 hour in 230～240 ℃, 250～260 ℃, 280～290 ℃, 310～320 ℃ temperature ranges in the aforesaid method; When the end capped crosslinkable Polyphenylene Sulfone of preparation propenyl, described repeatedly temperature control reaction is at 140～150 ℃, 160～170 ℃ temperature range internal reaction 1～3h.
The structural formula following (corresponding embodiment 5,6) of the end capped crosslinkable Polyphenylene Sulfone of propenyl of this patent preparation:
(III) n is the positive integer greater than 1
Corresponding embodiment 7,8:
(IV) n is the positive integer greater than 1
The building-up reactions formula one of polymkeric substance: (embodiment 1,2)
The building-up reactions formula two of polymkeric substance: (embodiment 3,4)
The building-up reactions formula three of polymkeric substance: (embodiment 5,6)
The building-up reactions formula four of polymkeric substance: (embodiment 7,8)
Novel polyphenyl sulfone high performance structures material by the method for the invention preparation and contain the end capped crosslinkable Polyphenylene Sulfone of propenyl structure high performance material and have two significant advantages.
One, by the nucleophilic substitution route, successfully prepared Polyphenylene Sulfone high-performance polymer structured material;
Two,, realize the further raising of p-poly-phenyl sulfone high-performance polymer performance by utilizing crosslinkable propenyl structure p-poly-phenyl sulfone oligopolymer to carry out end-blocking.Because therefore the temperature lower (being lower than 200 ℃) of propenyl structure generation crosslinking reaction, makes the further raising and the improvement that contain the end capped Polyphenylene Sulfone material property of propenyl structure become practical, has widened the use range and the process window of such material.
Description of drawings
The DSC curve of the Polyphenylene Sulfone polymkeric substance (PPSU) of Fig. 1: embodiment 1 preparation;
The thermogravimetric curve of the Polyphenylene Sulfone polymkeric substance (PPSU) of Fig. 2: embodiment 1 preparation
The infrared spectrogram of the Polyphenylene Sulfone polymkeric substance (PPSU) of Fig. 3: embodiment 1 preparation.
Embodiment
Embodiment 1:
Mechanical stirring is being housed, add 43.64g (0.20mol) 4 in the 1000ml three-necked bottle of thermometer and logical nitrogen, 4 '-difluoro benzophenone, 4,4 '-dihydroxy diphenylsulphone 50.05g (0.20mol), the solid content of sulfobenzide calculates according to 30%, need 200.83g (0.92mol) sulfobenzide, (it is (43.64+50.05-2 * 0.02 * 19) * 70/30=200.83) that method is calculated, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stirring is warming up to 240 ℃ of reaction 2h, be warming up to 260 ℃ of reaction 1h, be warming up to 290 ℃ of reaction response 1h, last elevated temperature to 310 ℃ continuation reaction 3h, reaction product discharging in cold water (room temperature), thick product is pulverized (200 order) through pulverizer, respectively with acetone and distilled water boiling washing 6～8 times to remove organic solvent sulfobenzide and inorganic salt, final product obtains white Polyphenylene Sulfone powdered sample 83.49g, productive rate 97% at 120 ℃ of dry 12h.Viscosimetry is surveyed its molecular weight about 40,000, the DSC result of study shows, the second-order transition temperature of the polyetherketone of present embodiment preparation is 230 ℃, the thermal weight loss result shows that its thermal weight loss 5% temperature is 530 ℃, its structural formula is shown in (I), in the infrared spectrogram shown in Figure 3, wave number (X-coordinate, the cm of unit
-1) at 2593cm
-1With 2444cm
-1The place is sulfuryl absorption peak, 1582cm
-1Be carbonyl absorption peak, 1591 is carbon-carbon double bond absorption peak in the phenyl ring, and 1236 is the absorption peak of ehter bond between phenyl ring, and 717 and 826 is the absorption peak of hydrocarbon key on the phenyl ring.
Embodiment 2:
Method such as embodiment 1, change 4 successively, the molar content of 4 '-difluoro benzophenone is 0.201mol, 0.202mol, 0.203mol, 0.204mol, after the processing identical with embodiment 1, obtain the Polyphenylene Sulfone white powder sample of molecular weight between 30,000 to 50,000 respectively, all between 96%～98%, its structural formula is shown in (I) for the productive rate of gained sample.
Embodiment 3:
Mechanical stirring is being housed, add 66.42g (0.20mol) 4 in the 1000ml three-necked bottle of thermometer and logical nitrogen, 4 '-difluoro triphen diketone, 4,4 '-dihydroxy benzophenone 50.05g (0.20mol), the solid content of sulfobenzide calculates according to 30%, need 254.03g (1.17mol) sulfobenzide, method of calculation are with embodiment 1, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stir and be warming up to 240 ℃ of reaction 1h, rising temperature of reaction, be controlled at 260 ℃ respectively, 290 ℃ are respectively reacted 1h, elevated temperature to 310 ℃ continuation reaction 3h, reaction product is discharging in cold water, and thick product is pulverized through pulverizer, respectively with acetone and distilled water boiling washing 6～8 times to remove organic solvent and inorganic salt, final product obtains white polymer powdered sample 106.70g, productive rate 98% at 120 ℃ of dry 12h.The molecular weight of polymkeric substance is about 40,000, and its structural formula is shown in (II).
Embodiment 4:
Method such as embodiment 3, change 4 successively, the molar content of 4 '-difluoro triphen diketone is 0.201mol, 0.202mol, 0.203mol, 0.204mol, after the processing identical with embodiment 3, obtain the polymkeric substance white powder sample of molecular weight between 30,000 to 50,000 respectively, all between 96%～98%, its structural formula is shown in (II) for the productive rate of gained sample.
Embodiment 5:
Mechanical stirring is being housed, add 45.82g (0.21mol) 4 in the 1000ml three-necked bottle of thermometer and logical nitrogen, 4 '-difluoro benzophenone, 4,4 '-dihydroxy benzophenone 50.05g (0.20mol), 200.83g (0.92mol) sulfobenzide, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stirring is warming up to 240 ℃ of reaction 2h, be warming up to 260 ℃ of reaction 1h, be warming up to 290 ℃ of reaction response 1h, last elevated temperature to 310 ℃ continuation reaction 3h, reaction product is discharging in cold water, thick product is pulverized through pulverizer, respectively with acetone and distilled water boiling washing 6～8 times to remove organic solvent and inorganic salt, final product obtains white Polyphenylene Sulfone oligopolymer powdered sample 83.49 grams at 120 ℃ of dry 12h, productive rate 97%, molecular weight is about 10,000.
Under the room temperature Polyphenylene Sulfone oligopolymer 20g joined (solid content is 30%) in the 70ml N-Methyl pyrrolidone organic solvent, after the heating for dissolving, add the bifunctional monomer's compound 2 that contains the propenyl structure, 2 '-diallyl dihydroxyphenyl propane 15.41g (0.05mol) and 7.25g (0.0525mol) salt of wormwood catalyzer, stirring is warming up to 140 ℃ of reaction 2h, 3h is reacted in elevated temperature to 160 a ℃ continuation then, reaction product is discharging in cold water, thick product is pulverized through pulverizer, the powdered sample that obtains with washing with alcohol 6 times to remove organic solvent, then with the distilled water boiling washing to remove inorganic salt, final product is at 110 ℃ of dry 12h, obtain the end capped crosslinkable Polyphenylene Sulfone of white propenyl polymer powder sample 28 grams, productive rate is 98%, 2, this embodiment oligomer molecule amount of molecular weight ratio of 2 '-diallyl dihydroxyphenyl propane end-blocking Polyphenylene Sulfone oligopolymer is big by 615.Its structural formula is shown in (III).
Embodiment 6:
Method such as embodiment 5, change 4 successively, the molar content of 4 '-difluoro benzophenone is 0.216mol, 0.220mol, 0.224mol, 0.230mol, through the process identical with embodiment 5, obtain the end capped crosslinkable Polyphenylene Sulfone of the propenyl of molecular weight between 30,000 to 50,000 polymer powder art sample respectively, all between 96%～98%, its structural formula is shown in (III) for the productive rate of gained sample.
Embodiment 7:
Mechanical stirring is being housed, add 69.74g (0.21mol) 4 in the 1000ml three-necked bottle of thermometer and logical nitrogen, 4 '-difluoro triphen diketone, 4,4 '-dihydroxy benzophenone 50.05g (0.20mol), 254.03g (1.17mol) sulfobenzide, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stirring is warming up to 240 ℃ of reaction 2h, be warming up to 260 ℃ of reaction 1h, be warming up to 290 ℃ of reaction response 1h, last elevated temperature to 310 ℃ continuation reaction 3h, reaction product is discharging in cold water, thick product is pulverized through pulverizer, respectively with acetone and distilled water boiling washing 6 times to remove organic solvent and inorganic salt, final product obtains white Polyphenylene Sulfone oligopolymer powder art sample 108.82 grams at 120 ℃ of dry 12h, productive rate 97%, molecular weight is about 10,000.。
Under the room temperature Polyphenylene Sulfone oligopolymer 20g is joined in the N-Methyl pyrrolidone organic solvent, after the heating for dissolving, add the bifunctional monomer's compound 2 that contains the propenyl structure, 2 '-diallyl dihydroxyphenyl propane 15.41g (0.05mol) and 7.25g (0.0525mol) salt of wormwood catalyzer, stirring is warming up to 140 ℃ of reaction 2h, 3h is reacted in elevated temperature to 160 a ℃ continuation then, reaction product is discharging in cold water, thick product is pulverized through pulverizer, the powdered sample that obtains with washing with alcohol 6 times to remove organic solvent, then with distilled water boiling washing 6 times to remove inorganic salt, final product obtains the end capped crosslinkable Polyphenylene Sulfone of white propenyl polymer powder sample 27.5 grams at 110 ℃ of dry 12h, and productive rate is 97%, 2, this embodiment oligopolymer of molecular weight ratio of 2 '-diallyl dihydroxyphenyl propane end-blocking Polyphenylene Sulfone oligopolymer is big by 615.Its structural formula is shown in (IV).
Embodiment 8:
Method such as embodiment 7, change 4 successively, the molar content of 4 '-difluoro triphen diketone is 0.216mol, 0.220mol, 0.224mol, 0.230mol, through the process identical with embodiment 7, obtain the end capped crosslinkable Polyphenylene Sulfone of the propenyl of molecular weight between 30,000 to 50,000 polymer powder sample respectively, the productive rate of gained sample is all between 96%～98%.Its structural formula is shown in (IV).
Embodiment 9:
Change organic solvent among the embodiment 5 to embodiment 8 into tetramethylene sulfone, obtain identical or close result.
Claims (9)
1. Polyphenylene Sulfone polymkeric substance, its structural formula is as follows:
Or
N represents the polymerization degree, for greater than 1 integer.
2. method for preparing claim 1 Polyphenylene Sulfone polymkeric substance, the steps include: under the room temperature mol ratio be 1～1.03: 14,4 '-difluoro benzophenone or 4,4 '-difluoro triphen diketone and 4,4 '-dihydroxy diphenylsulphone joins in organic solvent sulfobenzide or the tetramethylene sulfone, and the solid content in the reaction system is 20%～35%, behind the heating and melting, add molar weight with respect to 4, the salt of wormwood of 4 '-dihydroxy diphenylsulphone excessive 3～5% is made catalyzer; Stirring heats up and carries out repeatedly getting polymer product after the temperature control reaction, with polymer product discharging in cold water, thick product is pulverized through pulverizer, the powdered sample that obtains with ethanol or washing with acetone repeatedly to remove organic solvent, then with the distilled water boiling washing repeatedly to remove inorganic salt, final product obtains white Polyphenylene Sulfone polymer powder at 110～120 ℃ of drying 10～15h.
3. the method for preparing the Polyphenylene Sulfone polymkeric substance as claimed in claim 2, it is characterized in that: repeatedly the temperature control reaction is meant in stirring temperature-rise period, constant or in very little scope, change at a certain temperature place control temperature of reaction system, carry out the reaction of certain hour then, question response makes the temperature of reaction system be increased to temperature of reaction next time rapidly after finishing again.
4. the method for preparing the Polyphenylene Sulfone polymkeric substance as claimed in claim 3, it is characterized in that: repeatedly the temperature control reaction is to carry out 2～5 times temperature control reaction in 200～320 ℃ of temperature ranges, the temperature interval of per twice temperature control reaction is 10～50 ℃, the time of each temperature control reaction is 1～5 hour, and the temperature control scope of each temperature control reaction is 5～10 ℃.
5. the method for preparing the Polyphenylene Sulfone polymkeric substance as claimed in claim 4, it is characterized in that: repeatedly the temperature control reaction is to react respectively 1～3 hour in 230～240 ℃, 250～260 ℃, 280～290 ℃ temperature ranges, at 310～320 ℃ of temperature range internal reaction 3～5h.
6. the end capped crosslinkable Polyphenylene Sulfone of propenyl, its structural formula is as follows:
Or
N represents the polymerization degree, for greater than 1 integer.
7. a method for preparing the end capped crosslinkable Polyphenylene Sulfone of the described propenyl of claim 6 the steps include:
The first step be at room temperature be with mol ratio 1.05～1.15: 14,4 '-difluoro benzophenone or 4,4 '-difluoro triphen diketone and 4,4 '-dihydroxy diphenylsulphone joins in the organic solvent sulfobenzide, solid content is 20%～30%, behind the heating and melting, add molar weight with respect to 4, the salt of wormwood catalyzer of 4 '-dihydroxy diphenylsulphone excessive 3～5%; After stirring intensification and carrying out repeatedly the temperature control reaction, with the discharging in cold water of gained Polyphenylene Sulfone oligopolymer, thick product is pulverized through pulverizer, the powdered sample that obtains with ethanol or washing with acetone to remove organic solvent, then with the distilled water boiling washing to remove inorganic salt, final product obtains white Polyphenylene Sulfone oligopolymer powder at 110～120 ℃ of drying 10～15h;
Second step was under room temperature the Polyphenylene Sulfone oligopolymer to be joined in organic solvent N-Methyl pyrrolidone or the tetramethylene sulfone, solid content is 20%～30%, after the heating for dissolving, adding molar weight is the bifunctional monomer's compound 2 that contains the propenyl structure of 1.03～1.05 times of Polyphenylene Sulfone oligopolymers, 2 '-diallyl dihydroxyphenyl propane; Add molar weight again with respect to 2, the salt of wormwood catalyzer of 2 '-diallyl dihydroxyphenyl propane excessive 3～5%, after stirring intensification and carrying out repeatedly the temperature control reaction, with products obtained therefrom discharging in cold water, thick product is pulverized through pulverizer, the powdered sample that obtains with ethanol or washing with acetone to remove organic solvent, then with the distilled water boiling washing to remove inorganic salt, final product obtains the end capped crosslinkable Polyphenylene Sulfone of white propenyl powder at 110～120 ℃ of drying 10～15h.
8. the method for preparing the end capped crosslinkable Polyphenylene Sulfone of propenyl as claimed in claim 7, it is characterized in that: during preparation Polyphenylene Sulfone oligopolymer, described repeatedly temperature control reaction is to carry out 2～5 temperature control reactions in 200～320 ℃ of temperature ranges, per twice temperature control temperature of reaction is spaced apart 10～50 ℃, each temperature control reaction 1～5 hour, the temperature range of each temperature control reaction is 5～10 ℃; During the end capped crosslinkable Polyphenylene Sulfone of preparation propenyl, described repeatedly temperature control reaction is to carry out 2～3 temperature control reactions in 140～180 ℃ of temperature ranges, per twice temperature control temperature of reaction is spaced apart 10～20 ℃, each temperature control reaction 1～3 hour, and the temperature range of each temperature control reaction is 5～10 ℃.
9. the method for preparing the end capped crosslinkable Polyphenylene Sulfone of propenyl as claimed in claim 8, it is characterized in that: during preparation Polyphenylene Sulfone oligopolymer, described repeatedly temperature control reaction is to react respectively 1～5 hour in 230～240 ℃, 250～260 ℃, 280～290 ℃, 310～320 ℃ temperature ranges; During the end capped crosslinkable Polyphenylene Sulfone of preparation propenyl, described repeatedly temperature control reaction is at 140～150 ℃, 160～170 ℃ temperature range internal reaction 1～3h.
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| CNA2007100561171A CN101139441A (en) | 2007-09-29 | 2007-09-29 | Novel polysulfoneamide and acrylic terminated crosslinkable polysulfoneamide and preparation method thereof |
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| CN102824678A (en) * | 2011-06-17 | 2012-12-19 | 通用电气公司 | Anesthesia vaporizer system |
| CN103992472A (en) * | 2014-05-22 | 2014-08-20 | 吉林大学 | Polyether ketone resin and method for preparing same by polymerization termination |
| CN104015382A (en) * | 2014-05-12 | 2014-09-03 | 宁波爱乐宝婴儿用品有限公司 | Production process of PPSU (Polyphenylsulphone) milk bottle |
| CN109942808A (en) * | 2019-03-07 | 2019-06-28 | 东北师范大学 | A kind of poly(aryl ether ketone) and preparation method thereof and the application in lithium battery diaphragm |
| CN113015758A (en) * | 2018-06-27 | 2021-06-22 | 沙特高性能聚合物和塑料全球技术公司 | Semi-crystalline polyphenylsulfone and related methods of manufacture and additive manufacturing methods |
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- 2007-09-29 CN CNA2007100561171A patent/CN101139441A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102824678A (en) * | 2011-06-17 | 2012-12-19 | 通用电气公司 | Anesthesia vaporizer system |
| CN104015382A (en) * | 2014-05-12 | 2014-09-03 | 宁波爱乐宝婴儿用品有限公司 | Production process of PPSU (Polyphenylsulphone) milk bottle |
| CN103992472A (en) * | 2014-05-22 | 2014-08-20 | 吉林大学 | Polyether ketone resin and method for preparing same by polymerization termination |
| CN103992472B (en) * | 2014-05-22 | 2016-03-02 | 吉林大学 | The preparation method that a kind of polyether ketone resin and polymerization thereof stop |
| CN113015758A (en) * | 2018-06-27 | 2021-06-22 | 沙特高性能聚合物和塑料全球技术公司 | Semi-crystalline polyphenylsulfone and related methods of manufacture and additive manufacturing methods |
| US11512169B2 (en) | 2018-06-27 | 2022-11-29 | Shpp Global Technologies B.V. | Semicrystalline polyphenylsulfone and associated method of making and method of additive manufacturing |
| CN109942808A (en) * | 2019-03-07 | 2019-06-28 | 东北师范大学 | A kind of poly(aryl ether ketone) and preparation method thereof and the application in lithium battery diaphragm |
| CN109942808B (en) * | 2019-03-07 | 2021-04-23 | 东北师范大学 | Polyaryletherketone, preparation method thereof and application thereof in lithium battery diaphragm |
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