CN1557856A - Poly-aryl ether ketone performed polymers terminated with phenyl-ethynyl, preparation method therefor and crosslinked materials using the same - Google Patents
Poly-aryl ether ketone performed polymers terminated with phenyl-ethynyl, preparation method therefor and crosslinked materials using the same Download PDFInfo
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Abstract
The present invention is one new kind of phenylethynyl blocked polyaryl ether ketone pre-polymer and its preparation process and application in preparing high performance cross-linking material. Halogen substitured benzophenone compound is first prepared and then made to coupled with phenyl acetylene under the catalysis of Pd catalyst to prepare fluoric phenylethynyl blocked monomer, which is made to take nucleophilic substitution reaction with the branch unit of triphenol to synthesize the polyaryl ether ketone pre-polymer as phenylethynyl blocked branched compound. The branched compound may perform heat cross-liking reaction of the phenylethynyl radical at high temperature. The pre-polymer has excellent performance of forming spatial network structure via cross-linking.
Description
Technical field:
The invention belongs to polymeric material field, be specifically related to a kind of novel phenylacetylene end capacity capped polyaryletherketone performed polymer, the preparation method and the application of this performed polymer aspect preparation high-performance cross-linked material of this performed polymer.
Background technology:
Along with science and technology development, people are more and more higher to the requirement of material, and general-purpose plastics can not satisfy the increasingly extensive and urgent requirement of people, and this makes some high molecular scholars' work develop towards the polymkeric substance direction that preparation has excellent use properties.High performance engineering plastics is the special plastic of the excellent performance of being used widely in various engineerings field that grows up in the sixties.These plastics are generally classified according to working method, can be divided into two classes, and a class is a thermoplastic engineering plastic, can be subjected to thermal softening and cooling curing repeatedly, and its main polymer chain is a linear structure usually; Another kind of is the thermoset engineering plastics, and its resin forms netted three dimensional structure and curing molding heating, pressurizeing, add and taken place crosslinkedly under the solidifying agent situation.This two classes material all has advantage separately.Thermoplastic engineering plastic has excellent processing characteristics, but use temperature is lower, and relative processing temperature is then higher; The thermoset engineering plastics have higher use temperature, but have certain difficulty when the foundry goods of fixed processing size shape.
Introduce reactive group at polymkeric substance upper edge molecular backbone chain or at the end of the chain, can utilize the processing characteristics of the excellence of thermoplastic material fully, and after processing, obtain thermosetting material, and then can improve the temperature resistant grade that material uses by crosslinking curing.The present invention is based on this design philosophy, each the branch's end of the chain that can hot crosslinked phenylacetylene group be incorporated into ether ketone branching type performed polymer, utilize lower molecular weight and unique branched structure that is easy to take place crosslinking reaction of institute's synthetic compound, make crosslinked back material have the performance of a lot of excellences, and then the excellent specific property of thermoplasticity and thermoset engineering plastics organically is attached in the commaterial because of the cross-linked structure of its high crosslink density and the degree of depth.
Summary of the invention:
The purpose of this invention is to provide the preparation method of a kind of novel ether ketone branching type performed polymer with phenylacetylene-capped structure, this performed polymer and utilize this performed polymer to have the excellent specific property of thermoplasticity and thermoset engineering plastics, the application behind heat cross-linking aspect the preparation high-performance cross-linked material concurrently.
The structural formula of the phenylacetylene-capped branching type performed polymer of the present invention's design is:
The preparation method of phenylacetylene-capped branching type PAEK performed polymer involved in the present invention comprises following three steps: the preparation of the Benzophenones compound that halogen replaces, phenylacetylene-capped monomeric synthetic, phenylacetylene-capped polyaryletherketone performed polymer synthetic.The phenylacetylene-capped branching type performed polymer that finally obtains at high temperature carries out the heat cross-linking reaction, can obtain high performance heat cross-linking material.
(1) the Benzophenones compound of preparation halogen replacement
The Benzophenones compound that halogen replaces is to be raw material with the acyl chlorides monomer, and simultaneously as solvent and another kind of raw material, aluminum trichloride (anhydrous) is as catalyzer with excessive halogeno-benzene, and the Fu Shi acylation reaction prepares by taking place.Its structure and preparation method are:
Concrete technology comprises: add a certain amount of acyl chlorides and big excessive (mol ratio can be 3～20 times of acyl chlorides) fluorobenzene in the three-necked bottle that mechanical stirring, backflow band water device, hydrogen chloride gas absorption unit and nitrogen gangway are housed.Ice bath is cooled to and adds 1.2～2.0 times of excessive catalyzer aluminum trichloride (anhydrous)s after 0 ℃, rises to stirring at room 15min-20min post-heating to reflux temperature and stirs 3～6 hours, is cooled to stir reaction in 6～16 hours after the room temperature and finish.The speed that reaction finishes to drip with per second 1-2 the back drips 20～50ml distilled water to remove excessive aluminum chloride, eliminate behind the excessive fluorobenzene NaOH alkaline solution boiling washing product secondary with the azeotropic system of fluorobenzene/water with the 10%-20% weight percent concentration, and be neutral to filtrate 2-5 time further with distilled water boiling washing product, drying, thus the ethyl alcohol recrystallization purification obtains the Benzophenones compound.
(2) prepare phenylacetylene-capped monomer
Phenylacetylene-capped monomer is to utilize fragrant bromo-derivative under the palladium catalysis (that is: the Benzophenones compound of halogen replacement) and wait the preparation of a mole phenylacetylene generation coupled reaction.Catalyst system therefor comprises inferior ketone of triphenylphosphine palladium chloride, triphenylphosphine, iodate and triethylamine, and wherein triethylamine had not only been made catalyzer but also as solvent.Its structure and preparation method are (referring to document: R.G.Bryant, B.J.Jensen, and P.M.Hergenrother, Polym.Prepr., 33 (1), 910 (1992)):
Concrete technology comprises: in the three-necked bottle that mechanical stirring, reflux condensing tube and nitrogen gangway are housed, add benzophenone compound, 50～100ml triethylamine and catalytic amount that the 0.05mol halogen replaces triphenylphosphine palladium chloride (0.05～0.10g), triphenylphosphine (0.10～0.20g), the inferior ketone of iodate (0.05～0.10g), wash with the 150ml triethylamine.Reaction system is heated to 60 ℃, adds the 0.05mol phenylacetylene and also wash with 50～100ml triethylamine.Be warming up to 80 ℃ and stirred 4～8 hours, reduce to room temperature continue reaction after 8～16 hours after filtration, obtain product after the washing, recrystallization.
(3) phenylacetylene-capped polyaryletherketone performed polymer is synthetic
The synthetic method of phenylacetylene-capped branch's performed polymer is as follows among the present invention: utilize triphenol monomer (1,3, the 5-trihydroxybenzene) as cladon, phenylacetylene-capped fluorochemical monomer as another kind of raw material, DMAC is a solvent, Anhydrous potassium carbonate is as catalyzer, via fragrant nucleophilic substitution route, and three branches, phenylacetylene-capped performed polymer have been prepared by method in the fluorine-containing alkynes monomer that the triphenol monomer utmost point is splashed into stoichiometric ratio at a slow speed.Thereby this method can guarantee that sufficient reacting carries out in the instantaneous monomeric high concentration of fluorine-containing alkynes that causes that the triphenol monomer splashes into, and resulting monomer is branch rather than linear product.Its structure and reaction equation are:
Specific embodiment comprises: mechanical stirring be housed, add in the three-necked bottle of reflux band water device and nitrogen gangway more than the triplication triphenol monomer (0.024～0.48mol) phenylacetylene-capped monomer (being product prepared in the step 2), catalyzer Anhydrous potassium carbonate (0.012～0.036mol), a large amount of DMAC (120～200ml) and a spot of toluene (30～50ml).The system for the treatment of be heated to reflux and band water 2 hours after, (20～50ml) solution splash in the reaction system with (1/3～6 seconds) at a slow speed with the monomeric DMAC of the triphenol of 0.008mol, keep refluxing and be with water, dropwise back continuation reaction and made it to react completely in 12～48 hours.
Reaction mixture discharging to a large amount of HCl aqueous solution (in 1000～3500ml), are obtained faint yellow flocks, this sedimentation and filtration, dry back are washed 2～3 times repeatedly with ethanol, dry in baking oven, obtain thick product after leaving standstill.This thick product is obtained milky phenylacetylene-capped branch's performed polymer through the DMAC recrystallization.
Branch's performed polymer of the present invention's preparation has solubility, the processing characteristics excellence, and the use temperature and the comparable common engineering plastics of temperature classification of the crosslinked back of elevated temperature heat material improve about 100 ℃.
(4) heat cross-linking of polyaryletherketone performed polymer reaction
On the basis of phenylacetylene-capped polyaryletherketone performed polymer by thermal treatment certain hour at high temperature, obtained the network-like polymer materials after crosslinked.
Specific embodiment comprises: prepared phenylacetylene-capped branching type performed polymer in the step (3) is dissolved among the DMAC (or directly the performed polymer powder is uniformly distributed in treat fusion thermal treatment on the silicon chip), thermal treatment made chainpropagation, the branch, crosslinked of phenylacetylene group experience free radical mechanism in 0～2 hour under 300～380 ℃ high temperature, became spatial network shape structure up to being cross-linked with each other.
Description of drawings
Fig. 1: phenylacetylene-capped monomeric DSC scintigram;
Fig. 2 (1), Fig. 2 (2): phenylacetylene-capped monomeric nuclear magnetic spectrogram;
Fig. 3: phenylacetylene-capped monomeric laser desorption flight time mass spectrum figure;
Fig. 4: the DSC scintigram of the phenylacetylene-capped performed polymer of branching type;
Fig. 5: the laser desorption flight time mass spectrum figure of the phenylacetylene-capped performed polymer of branching type;
Fig. 6: the DSC intensification scintigram of cross-linked polymer;
Fig. 7: the dynamic mechanical analysis of cross-linked polymer (DMA) graphic representation;
Fig. 8 (1): the thermal weight loss of cross-linked polymer (TGA) graphic representation under air;
Fig. 8 (2): the thermal weight loss of cross-linked polymer (TGA) graphic representation under nitrogen.
As shown in Figure 1, be the DSC scintigram of phenylacetylene-capped monomer, we can find out benzene by this figure The fusing point of acetylene end-blocking monomer is 159 ℃, and the data of this and bibliographical information meet substantially.
Grind by the calculating to the one dimension hydrogen nuclear magnetic spectrogram of the phenylacetylene-capped monomer of Fig. 2 (1) and Fig. 2 (2) Study carefully, we can roughly provide the ownership of hydrogen.
Fig. 3 is the laser desorption flight time mass spectrum figure of phenylacetylene-capped monomer, wherein, and (M+H+〕＝301.0，
〔M+Na
+)=323.0, by the molecular ion peak among the figure as can be known, we obtained the set goal product--phenylacetylene-capped monomer.
The elementary analysis data of phenylacetylene-capped monomer are as follows:
Theoretical: C:83.98%; H:4.36%
Actual measurement: C:84.28%; H:4.51%
To sum up, by DSC, nuclear-magnetism and three kinds of characterization methods of mass spectrum, proved target product---phenylacetylene The existence of end-blocking monomer and monodispersity; By the elementary analysis data, proved the higher degree of this product.
As shown in Figure 4, be the DSC scintigram of the phenylacetylene-capped performed polymer of branching type, we can by this figure Take the fusing point of finding out this performed polymer as 252 ℃, and a wide crosslinked exothermic peak appears at 403 ℃ of temperature places, Wider temperature range has proved that also this performed polymer is in crosslinked bigger adding when becoming network polymers between two peaks Worker's window.
Fig. 5 is the laser desorption flight time mass spectrum figure of the phenylacetylene-capped performed polymer of branching type, wherein, and (M+H+〕
＝968.0，〔M+Na
+〕＝990.0，〔M+K
+)=1006.0, by the molecular ion peak among the figure as can be known, I Obtained the set goal product---the phenylacetylene-capped performed polymer of branching type.
The elementary analysis data of the phenylacetylene-capped performed polymer of branching type:
Theoretical: C:85.70%; H:4.38%; O:9.93%
Actual measurement: C:85.53%; H:4.58%; O:9.66%
To sum up, by DSC and two kinds of characterization methods of mass spectrum, proved target product---the branching type phenylacetylene Existence and the monodispersity of the PAEK performed polymer of end-blocking; By the elementary analysis data, proved this product High-purity.
As shown in Figure 6, in melting peak and the heat release of measuring phenylacetylene-capped performed polymer by the DSC single pass After the peak, rescan is carried out in annealing, further analyzes the thermal behavior of crosslinked rear polymer.
Fig. 7 is dynamic mechanical analysis (DMA) curve map of crosslinked rear polymer, after this curve demonstration is crosslinked Film its more than Tg (more than 400 ℃) still have higher modulus to keep, this show crosslinked rear material can Up to using under the high temperature more than 400 ℃.
Shown in Fig. 8 (1) and Fig. 8 (2), be respectively crosslinked rear thin polymer film under air and nitrogen No matter TGA curve map, visible crosslinked rear polymer are that 5% thermal weight loss temperature under air or under the nitrogen all can Reach about 500 ℃, this has shown that this material has excellent heat endurance and thermo oxidative stability.
To sum up, by crosslinked rear polymeric material is carried out performance test, prove the branching type that we synthesize Phenylacetylene-capped performed polymer at high temperature carries out having obtained high performance heat cross-linking material after the heat cross-linking reaction.
Embodiment
The specific embodiment of the Benzophenones compound that halogen replaces:
Embodiment 1:
In the three-necked bottle that mechanical stirring, backflow band water device, hydrogen chloride gas absorption unit and nitrogen gangway are housed, add 39.8g (0.18mol) parabromobenzoyl chloride and 8 times of excessive 135ml fluorobenzene.Add 33.8g (0.25mol) catalyzer aluminum trichloride (anhydrous) after ice bath is cooled to 0 ℃, rise to stirring at room 15min left and right sides post-heating to reflux temperature and stirred 3～6 hours.Be cooled to and stir reaction in 6～16 hours after the room temperature and finish.The speed of dripping with 1 of per second after reaction finishes drips 20～50ml distilled water to remove excessive aluminum chloride, eliminate behind the excessive fluorobenzene NaOH alkaline solution boiling washing product secondary with the azeotropic system of fluorobenzene/water with 10% weight percent concentration, and be neutral to filtrate three times further with distilled water boiling washing product, drying, thus ethyl alcohol recrystallization obtains 43.3g (productive rate: the white plates crystal of 4-bromo-4 '-fluorine benzophenone 86.19%).
The embodiment of phenylacetylene-capped polyaryletherketone performed polymer preparation:
Embodiment 2:
1.008g triphenol monomer (0.008mol) is dissolved among the DMAC of 30ml.In the 250ml three-necked bottle that mechanical stirring, backflow band water device and nitrogen gangway are housed, add the fluorine-containing alkynes monomer (0.024mol) of 7.2g, the catalyzer Anhydrous potassium carbonate of 2.5g, DMAC and the 40ml toluene of 150ml in advance, system be heated to reflux and band water 2 hours after, the monomeric DMAC solution of pre-configured triphenol is splashed in the reaction system with the 4 seconds/speed of dripping, keep refluxing and be with water, dropwise the back and continue reaction 24 hours.The reaction solution discharging is to the HCl aqueous solution of 2000ml, after leaving standstill dark yellow sedimentation and filtration, dry back are washed 2 times repeatedly with ethanol, in baking oven, dry, the thick product of gained is obtained the oyster white product 6.80g (productive rate: 87.86%) of phenylacetylene-capped branch's performed polymer through the DMAC recrystallization.(fusing point: 252 ℃; The molecular weight that mass spectrometric measurement obtains (m/e): 967.7, the molecular weight of calculating: 967.1g/mol).
Embodiment 3:
Add reversed in order with the raw material of embodiment 2, other embodiment is identical, thereby the instantaneous high concentration that has caused triphenol that splashes at the alkynes monomer: the fluorine-containing alkynes monomer (0.024mol) of 7.2g is dissolved among the DMAC of 80ml, mechanical stirring is being housed, add 1.008g triphenol monomer (0.008mol) in advance in the 250ml three-necked bottle of backflow band water device and nitrogen gangway, 2.5g the catalyzer Anhydrous potassium carbonate, the DMAC of 150ml and 40ml toluene, system is heated to backflow and band water splashed into the monomeric DMAC solution of pre-configured triphenol in the reaction system with the 3 seconds/speed of dripping in 2 hours afterwards, keep refluxing and be with water, dropwise the back and continue reaction 12 hours.The reaction solution discharging is washed dark yellow sedimentation and filtration, dry back 2 times with ethanol after leaving standstill to the HCl aqueous solution of 2000ml repeatedly, dries in baking oven, and the thick product of gained is obtained light yellow product through the DMAC recrystallization.(fusing point: 299 ℃, be speculated as the incomplete linear product of triphenol monomer hydroxyl reaction, may be that its unreacted phenolic hydroxyl group has caused the formation of hydrogen bond, thereby fusing point is raise).
Embodiment 4:
Different with the raw material interpolation order of embodiment 2, embodiment 3, the triphenol and the fluorine-containing alkynes monomer that will react the metering ratio simultaneously join in the reaction system in advance: add the fluorine-containing alkynes monomer (0.024mol) of 1.008g triphenol monomer (0.008mol), 7.2g, the catalyzer Anhydrous potassium carbonate of 2.5g, DMAC and the 40ml toluene of 150ml in advance in the 250ml three-necked bottle that mechanical stirring, backflow band water device and nitrogen gangway are housed, system is heated to backflow, keeps this temperature 24 hours.The reaction solution discharging is to the HCl aqueous solution of 2000ml, after leaving standstill dark yellow sedimentation and filtration, dry back are washed 2 times repeatedly with ethanol, in baking oven, dry, the thick product of gained is obtained the oyster white product 5.95g (productive rate: 76.87%) of phenylacetylene-capped branch's performed polymer through the DMAC recrystallization.(fusing point: 252 ℃; The molecular weight that mass spectrometric measurement obtains (m/e): 967.7, the molecular weight of calculating: 967.1g/mol).
Embodiment 5:
With the same step of embodiment 2, the sustained reaction time lengthening to 48 after just will dripping hour, the productive rate that obtains the oyster white product of phenylacetylene-capped branch's performed polymer and embodiment 2 is close.
Embodiment 6:
With the same step of embodiment 2, the sustained reaction time after just will dripping foreshortens to 12 hours, obtains the oyster white product 6.35g (productive rate: 76.87%), be lower than the productive rate of embodiment 2 of phenylacetylene-capped branch's performed polymer.
Embodiment 7:
With the same step of embodiment 2, just the monomeric amount of fluorine-containing alkynes is increased to 14.4g (0.048mol), the productive rate that finally obtains the oyster white product of phenylacetylene-capped branch's performed polymer and embodiment 2 is close.
Embodiment 8:
With the same step of embodiment 2, just the amount with the catalyzer Anhydrous potassium carbonate increases to 5.0g (0.036mol), and the productive rate that finally obtains the oyster white product of phenylacetylene-capped branch's performed polymer and embodiment 2 is close.
The specific embodiment of the heat cross-linking reaction of polyaryletherketone performed polymer:
Embodiment 9:
Prepared phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, makes it in the heat cross-linking reaction of thermal treatment generation in 1 hour phenylacetylene group under 370 ℃ temperature on the silicon chip.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1The place does not observe the vibration absorption peak of phenylacetylene group, shows that performed polymer is crosslinked fully.
Embodiment 10:
Identical with the method for embodiment 9, just crosslinking temperature is reduced to 300 ℃, investigate the influence of temperature: prepared phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, makes it in the heat cross-linking reaction of thermal treatment generation in 1 hour phenylacetylene group under 300 ℃ temperature on the silicon chip to the crosslinking reaction degree.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1Still there is the vibration absorption peak of phenylacetylene group in the place, and it is crosslinked or crosslinked incomplete to show that performed polymer does not take place.
Embodiment 11:
Identical with the method for embodiment 9, just cross-linking reaction time was reduced to 0 hour, the investigation time is to the influence of crosslinking reaction degree: prepared phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, makes it in thermal treatment 0 hour under 370 ℃ temperature on the silicon chip.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1Still there is the vibration absorption peak of phenylacetylene group in the place, and it is crosslinked or crosslinked incomplete to show that performed polymer does not take place.
Embodiment 12:
Identical with the method for embodiment 9, just cross-linking reaction time was reduced to 10 minutes, the investigation time is to the influence of crosslinking reaction degree: prepared phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, makes it in thermal treatment 10 minutes under 370 ℃ temperature on the silicon chip.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1Still there is the vibration absorption peak of phenylacetylene group in the place, but absorption peak weakens to some extent than embodiment 11, show performed polymer taken place crosslinked but crosslinked not exclusively.
Embodiment 13:
Identical with the method for embodiment 9, just cross-linking reaction time was reduced to 20 minutes, the investigation time is to the influence of crosslinking reaction degree: prepared phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, makes it in thermal treatment 20 minutes under 370 ℃ temperature on the silicon chip.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1Still there is the vibration absorption peak of phenylacetylene group in the place, but absorption peak weakens to some extent than embodiment 12, show performed polymer taken place further crosslinked but crosslinked not exclusively.
Embodiment 14:
Identical with the method for embodiment 9, just cross-linking reaction time was reduced to 30 minutes, the investigation time is to the influence of crosslinking reaction degree: prepared phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, makes it in thermal treatment 30 minutes under 370 ℃ temperature on the silicon chip.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1Still there is the vibration absorption peak of phenylacetylene group in the place, but absorption peak weakens to some extent than embodiment 13, show performed polymer taken place further crosslinked but crosslinked not exclusively.
Embodiment 15:
Identical with the method for embodiment 9, just cross-linking reaction time is increased to 2 hours, the investigation time is to the influence of crosslinking reaction degree: prepared phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, makes it in thermal treatment 2 hours under 370 ℃ temperature on the silicon chip.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1The place does not observe the vibration absorption peak of phenylacetylene group yet, shows that performed polymer is crosslinked fully.Prolong cross-linking reaction time resulting cross-linked polymer is not had influence substantially.
Embodiment 16:
Identical with the crosslinking reaction condition of embodiment 9, change heat treated concrete grammar: prepared phenylacetylene-capped branching type performed polymer powder is uniformly distributed in treats fusion thermal treatment on the silicon chip, make it the heat cross-linking reaction of thermal treatment generation in 1 hour phenylacetylene group under 370 ℃ temperature.Silicon chip after handling is carried out infrared analysis, at 2210cm
-1The place does not observe the vibration absorption peak of phenylacetylene group, shows that performed polymer is crosslinked fully.As seen, for the crosslinking reaction of prepared performed polymer, no matter adopting solution method still is that scorification is heat-treated, and its best cross-linking reaction time is 1 hour, and best crosslinking reaction temperature is 370 ℃.
Claims (4)
1. phenylacetylene-capped poly aryl ether ketone performed polymer, it is characterized in that: in molecule, introduced a kind of branched structure that crosslinking reaction takes place that is easy to by the monomeric cladon of triphenol, and can hot crosslinked phenylacetylene group be incorporated into each branch's end of the chain of this branch compound, its structural formula is as follows:
2. method for preparing the described phenylacetylene-capped poly aryl ether ketone performed polymer of claim 1, comprise the preparation of the Benzophenones compound that halogen replaces, synthetic three steps of phenylacetylene-capped monomeric synthetic, phenylacetylene-capped branching type performed polymer, it is characterized in that:
(1) adding acyl chlorides and mol ratio are the fluorobenzene of 3～20 times of acyl chlorides in the three-necked bottle that mechanical stirring, backflow band water device, hydrogen chloride gas absorption unit and nitrogen gangway are housed, ice bath is cooled to and adds 1.2～2.0 times of excessive catalyzer aluminum trichloride (anhydrous)s after 0 ℃, rise to stirring at room 15min-20min post-heating to reflux temperature and stirred 3～6 hours, be chilled to and stir reaction in 6～16 hours after the room temperature and finish; The speed of dripping with per second 1-2 drips 20～50ml distilled water to remove excessive aluminum chloride, eliminate behind the excessive fluorobenzene NaOH alkaline solution boiling washing product secondary with the azeotropic system of fluorobenzene/water with the 10%-20% weight percent concentration, and be neutral to filtrate 2-5 time further with distilled water boiling washing product, drying, thus the ethyl alcohol recrystallization purification obtains the Benzophenones compound that halogen replaces;
(2) mechanical stirring is being housed, add the benzophenone compound that the 0.05mol halogen replaces in the three-necked bottle of reflux condensing tube and nitrogen gangway, 50～100ml triethylamine and catalyzer triphenylphosphine palladium chloride 0.05～0.10g, triphenylphosphine 0.10～0.20g, the inferior ketone 0.05～0.10g of iodate, wash with the 150ml triethylamine, reaction system is heated to 60 ℃, adding the 0.05mol phenylacetylene also washes with 50～100ml triethylamine, be warming up to 80 ℃ and stirred 4～8 hours, reduce to room temperature continue reaction after 8～16 hours after filtration, washing, obtain phenylacetylene-capped monomer product behind the recrystallization;
(3) in the three-necked bottle that mechanical stirring, backflow band water device and nitrogen gangway are housed, add the phenylacetylene-capped monomer of 0.024～0.048mol, 0.012 the DMAC of～0.036mol catalyzer Anhydrous potassium carbonate, 120～200ml and the toluene of 30～50ml, the system for the treatment of is heated to backflow and is with water after 2 hours, the monomeric DMAC solution of the triphenol of 0.008mol 20～50ml is splashed in the reaction system with 3～6 seconds/speed, keep refluxing and be with water, dropwise back continuation reaction and made it to react completely in 12～48 hours; In the HCI aqueous solution with reaction mixture discharging to 1000～3500ml, obtain faint yellow flocks after leaving standstill, this sedimentation and filtration, dry back are washed 2～3 times repeatedly with ethanol, in baking oven, dry, obtain thick product, this thick product is obtained milky phenylacetylene-capped branch's performed polymer through the DMAC recrystallization.
3. phenylacetylene-capped poly aryl ether ketone performed polymer as claimed in claim 1 is in the application that is used to prepare aspect the high-performance cross-linked material.
4. method that phenylacetylene-capped poly aryl ether ketone performed polymer is used to prepare the high-performance cross-linked material, it is characterized in that: phenylacetylene-capped branching type performed polymer is dissolved among the DMAC, or directly the performed polymer powder is uniformly distributed in and treats fusion thermal treatment on the silicon chip, thermal treatment made chainpropagation, the branch, crosslinked of phenylacetylene group experience free radical mechanism in 0～2 hour under 300～380 ℃ high temperature, become spatial network shape structure up to being cross-linked with each other, thereby obtain crosslinked network-like polymer materials.
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|---|---|---|---|---|
| CN100360584C (en) * | 2005-01-07 | 2008-01-09 | 吉林大学 | Method of synthesizing fluorine containing superbranched light wave conductive material based on A2+B3 type monomer reaction |
| US8492507B2 (en) | 2008-09-23 | 2013-07-23 | Nexam Chemical Ab | Acetylenic polyamide |
| CN102690181A (en) * | 2011-04-14 | 2012-09-26 | 京东方科技集团股份有限公司 | Liquid crystal low polymer, composition for synthesis, preparation method and liquid crystal material |
| US8952200B2 (en) | 2011-04-14 | 2015-02-10 | Boe Technology Group Co., Ltd. | Liquid crystal oligomer, synthesis composition, preparation method thereof, and liquid crystal material |
| CN107955158A (en) * | 2016-10-14 | 2018-04-24 | 徐州工程学院 | A kind of siliceous main chain aryl oxide ketone copolymers and preparation method thereof |
| CN106842819A (en) * | 2016-12-28 | 2017-06-13 | 杭州福斯特光伏材料股份有限公司 | One kind is containing alkynyl monomers end-blocking and developer solution selects flexible positive type photosensitive polyimide resin composition |
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