CN101186695A - Soluble fluorine-containing polyaryl ether ketone high-performance material, preparation method thereof and mixed film of the same and epoxy resin - Google Patents
Soluble fluorine-containing polyaryl ether ketone high-performance material, preparation method thereof and mixed film of the same and epoxy resin Download PDFInfo
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- CN101186695A CN101186695A CNA2007100563158A CN200710056315A CN101186695A CN 101186695 A CN101186695 A CN 101186695A CN A2007100563158 A CNA2007100563158 A CN A2007100563158A CN 200710056315 A CN200710056315 A CN 200710056315A CN 101186695 A CN101186695 A CN 101186695A
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Abstract
The invention relates to a new fluorine polyaryletheretherketone soluble high-performance material, a preparation method and a blend film material formed with epoxide resin. The preparation method comprises the following procedures regarding 4,4'- difluorobenzophenone or 4, 4'-difluorotribenzodiketone and mixing bisphenol monomer as the material, controlling the proportion of bisphenol hexaflurate A (or trifluoromethyl phenyl eldopaque) and bisphenol A ( or fenolftaleina) in the segment of polymer via the way of nucleophilic substitution reaction; getting the new fluorine polyaryletheretherketone soluble high-performance material, selecting the immobilized liquid epoxide resin and the functional polymer blend film prepared by the new fluorine polyaryletheretherketone soluble high-performance material in order to achieve the functionalization of polyaryletheretherketone material for meeting the aim of the different applying range and extending the processing window. The blend film material is suitable for high-performance composite material resin base field, microelectronic insulating material field, optical waveguide device field and air permoselective membrane field and the like.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the blended membrane material that a class soluble fluorine-containing polyaryl ether ketone high-performance material, this preparation methods and this material and Resins, epoxy form.
Background technology
The poly aryl ether ketone material has excellent physical chemistry as a kind of complete fragrant semicrystalline polymeric, thereby is widely used in fields such as electronic apparatus, machinery instrument, communications and transportation, aerospace.And polyether-ether-ketone (PEEK) also is widely used in various fields because it has excellent performance.For most of polyaryletherketone kinds,, cause closely piling up of molecular chain owing to reasons such as molecule chain rigidity, crystallinity, cause its solvability relatively poor, the melt temperature height can only adopt the method for hot briquetting, processing mode is single, has limited their application.But different needs along with application purpose and applied environment, the special engineering plastics of this type of excellent performance can not satisfy its demands of applications, in recent years, around improving processing characteristics, improve problems such as temperature classification, continually develop this type of novel material of excellent performance, to satisfy different service requirementss.For example on main polymer chain, introduce different functional groups (as naphthalene nucleus, azepine naphthalene nucleus etc.), will twist non-coplanar assorted naphthalene biphenyl structural and be incorporated into the solvability that to improve polymkeric substance in the main polymer chain, give the thermotolerance of polymkeric substance excellence simultaneously and on main chain, introduce side group functional group (as benzene, trifluoromethyl etc.) etc., improve the solvability of polyaryletherketone, perhaps further improve the use properties and the processing characteristics of material by modes such as copolymerization and blend.Wherein, fluorinated poly arylene ether ketone material can form strong chemical bond and have preferably electrical property etc. because fluorine element has stronger electronegativity, and size is less, makes it become extremely valuable substituting group in molecular designing.Fluorinated poly arylene ether ketone material has lower specific inductivity, refractive index and low water absorption, and can improve thermostability, solvability and flame retardant resistance, increase the material transparency, this base polymer is not only having important application prospects aspect the low-k microelectronics insulating material, and receive much concern in the research of Application Areass such as fiber waveguide device, photoelectron, optics and gas selective permeation film, have application potential.
The present invention is preparation soluble fluorine-containing polyaryl ether ketone high-performance material and this material and epoxy blend mould material, utilization contains fluorine structure and introduces thermostability, crystallinity and the solvability that the polyaryletherketone backbone structure can be improved polymkeric substance, reduces the water absorbability and the specific inductivity of polymkeric substance; The excellent properties that has kept the poly aryl ether ketone material simultaneously.Make this material combine the advantage of fluoropolymer and two kinds of materials of polyaryletherketone, both had good thermostability, solvability and flame retardant resistance, lower specific inductivity and water absorbability are arranged again.Successfully prepare soluble fluorine-containing polyaryl ether ketone high-performance material.And on this basis, a class novel fluorine polyaryletherketone and epoxy blend mould material have been prepared, the main application background of this blended membrane material is as the high performance composite resin matrix, because novel fluorine polyaryletherketone and Resins, epoxy have excellent solubility property, Resins, epoxy also give material certain stick performance, in preparation simple operation during matrix material, can simplify the operation of high-temperature shaping, keep the performance of resin matrix excellence simultaneously.For the high performance of poly aryl ether ketone material, expanded its use range and working method and have great practical value and develop value.
Summary of the invention
One of purpose of the present invention provides a kind of soluble fluorine-containing polyaryletherketone material of brand new;
Two of purpose of the present invention provides the soluble fluorine-containing polyaryletherketone preparation methods of above-mentioned brand new;
Three of purpose of the present invention provides the soluble fluorine-containing polyaryletherketone material of above-mentioned brand new and the blended membrane material that Resins, epoxy forms.
This patent is by the nucleophilic substitution reaction route, and regulation and control hexafluoro bisphenol-a (or m-trifluoromethylphenyl Resorcinol) and the ratio of dihydroxyphenyl propane (phenolphthalein) in polymer segment have been prepared soluble fluorine-containing polyaryl ether ketone high-performance material.Further, prepare functional polymer blending film, thereby reach the polyaryletherketone material functional to satisfy the purpose of different use range and expansion process window by selecting uncured liquid-state epoxy resin and above-mentioned soluble fluorine-containing polyaryletherketone.This blended membrane material can be used for high performance composite resin matrix, microelectronics insulating material, fiber waveguide device, gas-selectively through fields such as films.
The reaction process of soluble fluorine-containing polyaryletherketone is: under the room temperature be with mol ratio 1～1.03: 14,4 '-difluoro benzophenone (or position difluoro diketone, 4,4 '-difluoro triphen diketone) and the blended biphenol monomer join in organic solvent tetramethylene sulfone or the N-Methyl pyrrolidone (NMP), the blended biphenol monomer is meant and contains fluorine structure monomer hexafluoro bisphenol-a or m-trifluoromethylphenyl Resorcinol and dihydroxyphenyl propane or phenolphthalein [3, two (4-hydroxy phenyl)-1 (the 3H)-isobenzofuranones of 3-] and, solid content in the reaction system (solid content is meant that the quality that generates polymkeric substance accounts for the per-cent of polymkeric substance and solvent total mass) is 20%～30%, behind the heating and melting, add molar weight and make catalyzer with respect to the salt of wormwood that mixes biphenol monomer total mole number excessive 3～5%; Nitrogen protection; Stir and heat up, toluene is taken away the water that generates in the reaction process, emit toluene then, and carry 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 the distilled water boiling washing repeatedly to remove organic solvent and inorganic salt, final product obtains white poly aryl ether ketone polymer powdered 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 the temperature reaction process, 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, carry out reaction next time;
Further, repeatedly temperature control reaction described in the top method is to carry out 2～5 times temperature control reaction in 120～240 ℃ 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 120～130 ℃, 180～200 ℃ temperature ranges, to react respectively 1～3 hour, at 220～230 ℃ of temperature range internal reaction 3～5h.
Fluorinated poly arylene ether ketone and epoxy blend mould material, by mass, it contains 50～80% fluorinated poly arylene ether ketone, and all the other are liquid-state epoxy resin; It is to be 50～80%: 50～20% fluorinated poly arylene ether ketone and Resins, epoxy with mass percent, feed that to be hybridly prepared into mass percent concentration in (solvent ratio is easier to remove behind the film of shop) be 5～20% solution having more lower boiling tetrahydrochysene furan, adopt the method for curtain coating, spin coating or knifing to prepare thin-film material then, solvent flashing promptly obtains fluorinated poly arylene ether ketone and epoxy blend mould material at ambient temperature.
The polymer architecture general formula:
X-o-Y-o
mX-o-Z-o
n
-X-：
-Y-：
-Z-：
M, n represent the polymerization degree, are positive integer
(I)
The polymer architecture formula that embodiment 1,2 obtains is as follows:
(II) m, n represent the polymerization degree, are positive integer
The polymer architecture formula that embodiment 3,4 obtains is as follows:
(III) m, n are positive integer
The polymer architecture formula that embodiment 5,6 obtains is as follows:
(IV) m, n are positive integer
The polymer architecture formula that embodiment 7,8 obtains is as follows:
(V) m, n are positive integer
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)
Soluble fluorine-containing polyaryl ether ketone high-performance material by the method for the invention preparation and this material and epoxy blend mould material have two significant advantages.
One, by the nucleophilic substitution route, successfully prepared series soluble fluorinated poly arylene ether ketone high-performance polymer structured material;
Two, soluble fluorine-containing polyaryletherketone and epoxy blend mould material combine the recreation performance of fluorinated poly arylene ether ketone material and the stickiness and the chemical property of Resins, epoxy, because the boiling point low (65.40 ℃) of selective solvent, solvent can be removed fully behind the film of shop, realizes the use range of fluorinated poly arylene ether ketone high-performance polymer and further improving of use properties.
Description of drawings
The DSC curve of the soluble fluorine-containing poly aryl ether ketone polymer of Fig. 1: embodiment 1 preparation;
The thermogravimetric curve of the soluble fluorine-containing poly aryl ether ketone polymer of Fig. 2: embodiment 1 preparation;
The stress-strain(ed) curve of the soluble fluorine-containing poly aryl ether ketone polymer of Fig. 3: embodiment 1 preparation.
Embodiment
Embodiment 1:
In being housed, the 1000ml three-necked bottle of mechanical stirring, thermometer and logical nitrogen adds 43.64g (0.20mol) 4 successively, 4 '-difluoro benzophenone, dihydroxyphenyl propane 50.05g (0.16mol), hexafluoro bisphenol-a 13.59g (0.04mol), tetramethylene sulfone 195ml (solid content is 30%), toluene 100ml, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stirring is warming up to 120 ℃ of reaction 2h, the water that reaction generates is taken out of fully, elevated temperature is emitted toluene to next temperature of reaction interval in temperature-rise period then.Be warming up to 200 ℃ of reaction 1h, last elevated temperature to 230 ℃ continuation reaction 3h, reaction product is discharging in cold water, thick product is pulverized through pulverizer, with distilled water boiling washing 6～8 times to remove organic solvent tetramethylene sulfone and inorganic salt, final product obtains white soluble fluorine-containing polyaryletherketone powdered sample 96.69 g, productive rate 97% at 120 ℃ of dry 12h.The GPC method is surveyed its molecular weight about 30,000, and the DSC result of study shows that the second-order transition temperature of the soluble fluorine-containing polyaryletherketone of present embodiment preparation is 153 ℃, and the thermal weight loss result shows that its thermal weight loss 5% temperature is 493 ℃.Experiments of Machanics result (table 1) illustrates that polymkeric substance has excellent mechanical property.
Table 1: the mechanical property of the soluble fluorine-containing polyaryletherketone of this example preparation
| Sample | Elongation at break (%) | Tensile strength (MPa) | Tensile modulus (Gpa) |
| Polymkeric substance | 55.2 | 66 | 2.13 |
Annotate: adopt the omnipotent mechanical test machine of Japanese Shimadzu AG-I type;
Batten size: 3.1160 * 4.0300 * 20.0000mm, draw speed 2mm/min.
Embodiment 2:
Method such as embodiment 1, keep 4, the mole number of 4 '-difluoro benzophenone constant (0.20mol), the molar content that changes hexafluoro bisphenol-a successively is 0.06mol, 0.08mol, 0.10mol, 0.12mol, and the molar content of dihydroxyphenyl propane is for becoming 0.14mol, 0.12mol, 0.10mol, 0.08mol successively, after the processing identical with embodiment 1, obtain the soluble fluorine-containing polyaryletherketone white powder sample of molecular weight between 30,000 to 40,000 respectively, productive rate is between 96%～98%.The thermal characteristics and the mechanical property of products obtained therefrom and embodiment 1 product are close.
Embodiment 3:
In being housed, 1 000ml three-necked bottle of mechanical stirring, thermometer and logical nitrogen adds 43.64g (0.20mol) 4,4 '-difluoro benzophenone, hexafluoro bisphenol-a 13.59g (0.04mol), phenolphthalein 50.93g (0.16mol), tetramethylene sulfone 200ml, toluene 100ml, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stirring is warming up to 120 ℃ of reaction 2h, and the water that reaction generates is taken out of fully, and elevated temperature is emitted toluene then.Be warming up to 200 ℃ of reaction 1h, last elevated temperature to 230 ℃ continuation reaction 3h, reaction product is discharging in cold water, thick product is pulverized through pulverizer, with distilled water boiling washing 6～8 times to remove organic solvent tetramethylene sulfone and inorganic salt, final product obtains the white soluble fluorine-containing polyaryletherketone powdered sample of molecular weight about 30,000, productive rate 97% at 120 ℃ of dry 12h.
Embodiment 4:
Method such as embodiment 3, keep 4, the mole number of 4 '-difluoro benzophenone constant (0.20mol), the molar content that changes hexafluoro bisphenol-a successively is 0.06mol, 0.08mol, 0.10mol, 0.12mol, and the molar content of phenolphthalein is for becoming 0.14mol, 0.12mol, 0.10mol, 0.08mol successively, after the processing identical with embodiment 3, obtain the polymkeric substance white powder sample of molecular weight between 30,000 to 40,000 respectively, the productive rate of gained sample is between 96%～98%.
Embodiment 5:
In being housed, the 1000ml three-necked bottle of mechanical stirring, thermometer and logical nitrogen adds 43.64g (0.20mol) 4,4 '-difluoro benzophenone, phenolphthalein 12.73g (0.04mol), m-trifluoromethylphenyl Resorcinol 40.67g (0.16mol), tetramethylene sulfone 210ml, toluene 100ml, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stirring is warming up to 120 ℃ of reaction 2h, and the water that reaction generates is taken out of fully, and elevated temperature is emitted toluene then.Be warming up to 200 ℃ of reaction 1h, last elevated temperature to 230 ℃ continuation reaction 3h, reaction product is discharging in cold water, thick product is pulverized through pulverizer, with distilled water boiling washing 6～8 times to remove organic solvent tetramethylene sulfone and inorganic salt, final product obtains the white soluble fluorine-containing polyaryletherketone powdered sample of molecular weight about 30,000, productive rate 98% at 120 ℃ of dry 12h.
Embodiment 6:
Method such as embodiment 5, keep 4, the mole number of 4 '-difluoro benzophenone constant (0.20mol), the molar content that changes phenolphthalein successively is 0.06mol, 0.08mol, 0.10mol, 0.12mol, and the molar content of m-trifluoromethylphenyl Resorcinol is for becoming 0.14mol, 0.12mol, 0.10mol, 0.08mol successively, through the process identical with embodiment 5, obtain the white polymer powdered sample of molecular weight between 30,000 to 40,000 respectively, the productive rate of gained sample is between 96%～98%.
Embodiment 7:
In being housed, the 1000ml three-necked bottle of mechanical stirring, thermometer and logical nitrogen adds 43.64g (0.20mol) 4,4 '-difluoro benzophenone, dihydroxyphenyl propane 9.13g (0.04mol), m-trifluoromethylphenyl Resorcinol 40.67g (0.16mol), tetramethylene sulfone 200ml, toluene 100ml, add 28.98g (0.21mol) Anhydrous potassium carbonate behind the heating and melting, stirring is warming up to 120 ℃ of reaction 2h, and the water that reaction generates is taken out of fully, and elevated temperature is emitted toluene then.Be warming up to 200 ℃ of reaction 1h, last elevated temperature to 230 ℃ continuation reaction 3h, reaction product is discharging in cold water, thick product is pulverized through pulverizer, with distilled water boiling washing 6～8 times to remove organic solvent tetramethylene sulfone and inorganic salt, final product obtains the white soluble fluorine-containing polyaryletherketone powdered sample of molecular weight about 30,000, productive rate 98% at 120 ℃ of dry 12h.
Embodiment 8:
Method such as embodiment 7, keep 4, the mole number of 4 '-difluoro benzophenone constant (0.20mol), changing the molar content that changes dihydroxyphenyl propane successively successively is 0.06mol, 0.08mol, 0.10mol, 0.12mol, and the molar content of m-trifluoromethylphenyl Resorcinol is for becoming 0.14mol, 0.12mol, 0.10mol, 0.08mol successively, through the process identical with embodiment 7, obtain the white polymer powdered sample of molecular weight between 30,000 to 40,000 respectively, the productive rate of gained sample is between 96%～98%.
Embodiment 9:
Method such as embodiment 1, with 4, position difluoro diketone between 4 '-difluoro benzophenone changes into, reaction ratio and reaction conditions are constant, obtain polymkeric substance shown in the general formula (I) equally.
Embodiment 10:
Method such as embodiment 1, with 4,4 '-difluoro benzophenone changes 4 into, 4-difluoro triphen diketone, reaction ratio and reaction conditions are constant, obtain polymkeric substance shown in the general formula (I) equally.
Embodiment 11:
(80～50: 20～50) being hybridly prepared into mass percent concentration is 5～20% solution according to certain quality per-cent for soluble fluorine-containing polyaryletherketone that embodiment 1 to 10 is obtained and Resins, epoxy E44, solvent is chosen as the tetrahydrofuran (THF) that has than lower boiling (65.40 ℃), and purpose is that solvent ratio is easier to remove behind the film of shop.The blended membrane material of preparation combines the recreation performance of fluorinated poly arylene ether ketone material and the stickiness and the chemical property of Resins, epoxy, because the boiling point of selective solvent is low, solvent is removed easily fully behind the film of shop.Realized the use range of fluorinated poly arylene ether ketone high-performance polymer and further improving of use properties.With the increase of content of epoxy resin, the stickiness of blended membrane material strengthens.
Resins, epoxy is divided into liquid-state epoxy resin and solid epoxy resin according to state of resin under the room temperature, and liquid-state epoxy resin all is fit to this patent and prepares soluble fluorine-containing polyaryletherketone and epoxy blend mould material.
Claims (10)
1. soluble fluorine-containing polyaryl ether ketone high-performance material, its structural formula is as follows:
X-o-Y-o
mX-o-Z-o
n
Wherein ,-X-:
Or
-Y-:
Or
-Z-:
Or
M, n represent the polymerization degree, are positive integer.
2. soluble fluorine-containing polyaryl ether ketone high-performance material as claimed in claim 1, it is characterized in that: structural formula is as follows,
3. soluble fluorine-containing polyaryl ether ketone high-performance material as claimed in claim 1, it is characterized in that: structural formula is as follows,
4. soluble fluorine-containing polyaryl ether ketone high-performance material as claimed in claim 1, it is characterized in that: structural formula is as follows,
5. soluble fluorine-containing polyaryl ether ketone high-performance material as claimed in claim 1, it is characterized in that: structural formula is as follows,
6. method for preparing the described soluble fluorine-containing polyaryl ether ketone high-performance material of claim 1, it is characterized in that: under the room temperature be with mol ratio 1～1.03: 14,4 '-difluoro benzophenone, between the position difluoro diketone or 4,4 '-difluoro triphen diketone and blended biphenol monomer join in organic solvent tetramethylene sulfone or the N-Methyl pyrrolidone, the blended biphenol monomer be meant hexafluoro bisphenol-a or m-trifluoromethylphenyl Resorcinol and dihydroxyphenyl propane or phenolphthalein and, the reaction system solid content is 20%～30%, behind the heating and melting, add molar weight and make catalyzer with respect to the salt of wormwood that mixes biphenol monomer total mole number excessive 3～5%; Nitrogen protection; stir and heat up; toluene is taken away the water that generates in the reaction process; emit toluene then, and carry out repeatedly getting polymer product after the temperature control reaction, with polymer product discharging in cold water; thick product is pulverized through pulverizer; repeatedly to remove organic solvent and inorganic salt, final product obtains white fluorinated poly arylene ether ketone polymer powdered sample at 110～120 ℃ of drying 10～15h to the powdered sample that obtains with the distilled water boiling washing.
7. a kind of method for preparing soluble fluorine-containing polyaryl ether ketone high-performance material as claimed in claim 6, it is characterized in that: repeatedly the temperature control reaction is to carry out 2～5 times temperature control reaction in 120～240 ℃ 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 ℃.
8. a kind of method for preparing soluble fluorine-containing polyaryl ether ketone high-performance material as claimed in claim 7, it is characterized in that: repeatedly the temperature control reaction is to react respectively 1～3 hour in 120～130 ℃, 180～200 ℃ temperature ranges, at 220～230 ℃ of temperature range internal reaction 3～5h.
9. fluorinated poly arylene ether ketone and epoxy blend mould material, it is characterized in that: by mass, contain 50～80% the described soluble fluorine-containing polyaryl ether ketone of claim 1, all the other are liquid-state epoxy resin.
10. fluorinated poly arylene ether ketone and epoxy blend mould material, it is characterized in that: by mass, contain any one described soluble fluorine-containing polyaryl ether ketone of claim 2 to 5 of 50～80%, all the other are liquid-state epoxy resin.
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| CN101864070A (en) * | 2010-07-02 | 2010-10-20 | 中山大学 | Soluble polyarylether with high glass transition temperature and synthetic method thereof |
| CN102585210A (en) * | 2012-02-22 | 2012-07-18 | 中国科学院长春应用化学研究所 | Phenolphthalein polyaryletherketone and preparation method thereof |
| CN103665283A (en) * | 2012-09-12 | 2014-03-26 | 北京师范大学 | Method of preparing polyaryletherketone |
| CN106832384A (en) * | 2016-12-23 | 2017-06-13 | 中国科学院长春应用化学研究所 | A kind of ketone foamed material of lateral group polyarylether containing phthalein and preparation method thereof |
| CN107964099A (en) * | 2017-11-06 | 2018-04-27 | 吉林大学 | A kind of polymer-based damping material with micro phase separation structure and its preparation method and application |
| CN109923147A (en) * | 2017-10-12 | 2019-06-21 | 株式会社吴羽 | The manufacturing method of poly(aryl ether ketone) |
| US11118053B2 (en) | 2018-03-09 | 2021-09-14 | Ticona Llc | Polyaryletherketone/polyarylene sulfide composition |
| US11352480B2 (en) | 2016-03-18 | 2022-06-07 | Ticona Llc | Polyaryletherketone composition |
| CN115304764A (en) * | 2022-09-20 | 2022-11-08 | 福州大学 | Epoxidized fluorine-containing polyarylether compound and preparation method thereof |
| WO2023216537A1 (en) * | 2022-05-07 | 2023-11-16 | 铜陵精达特种电磁线股份有限公司 | High-temperature self-crosslinking fluorine-containing polyaryletherketone and preparation method therefor, and coating and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864070A (en) * | 2010-07-02 | 2010-10-20 | 中山大学 | Soluble polyarylether with high glass transition temperature and synthetic method thereof |
| CN102585210A (en) * | 2012-02-22 | 2012-07-18 | 中国科学院长春应用化学研究所 | Phenolphthalein polyaryletherketone and preparation method thereof |
| CN103665283A (en) * | 2012-09-12 | 2014-03-26 | 北京师范大学 | Method of preparing polyaryletherketone |
| CN103665283B (en) * | 2012-09-12 | 2016-03-30 | 北京师范大学 | A kind of method preparing polyaryletherketone |
| US11352480B2 (en) | 2016-03-18 | 2022-06-07 | Ticona Llc | Polyaryletherketone composition |
| CN106832384B (en) * | 2016-12-23 | 2019-10-25 | 中国科学院长春应用化学研究所 | One kind ketone foamed material of lateral group polyarylether containing phthalein and preparation method thereof |
| CN106832384A (en) * | 2016-12-23 | 2017-06-13 | 中国科学院长春应用化学研究所 | A kind of ketone foamed material of lateral group polyarylether containing phthalein and preparation method thereof |
| CN109923147A (en) * | 2017-10-12 | 2019-06-21 | 株式会社吴羽 | The manufacturing method of poly(aryl ether ketone) |
| CN109923147B (en) * | 2017-10-12 | 2022-04-01 | 株式会社吴羽 | Method for producing polyaryletherketone |
| US11485821B2 (en) | 2017-10-12 | 2022-11-01 | Kureha Corporation | Method for producing polyaryletherketone |
| CN107964099A (en) * | 2017-11-06 | 2018-04-27 | 吉林大学 | A kind of polymer-based damping material with micro phase separation structure and its preparation method and application |
| US11118053B2 (en) | 2018-03-09 | 2021-09-14 | Ticona Llc | Polyaryletherketone/polyarylene sulfide composition |
| WO2023216537A1 (en) * | 2022-05-07 | 2023-11-16 | 铜陵精达特种电磁线股份有限公司 | High-temperature self-crosslinking fluorine-containing polyaryletherketone and preparation method therefor, and coating and preparation method therefor |
| CN115304764A (en) * | 2022-09-20 | 2022-11-08 | 福州大学 | Epoxidized fluorine-containing polyarylether compound and preparation method thereof |
| CN115304764B (en) * | 2022-09-20 | 2023-06-09 | 福州大学 | Epoxidized fluorine-containing polyarylether compound and preparation method thereof |
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