CN102660016A - 2,6-dihalo benzonitrile-4,4'dihalobenzophenone-phenolphthalein terpolymer and preparation method thereof - Google Patents
2,6-dihalo benzonitrile-4,4'dihalobenzophenone-phenolphthalein terpolymer and preparation method thereof Download PDFInfo
- Publication number
- CN102660016A CN102660016A CN2012100712420A CN201210071242A CN102660016A CN 102660016 A CN102660016 A CN 102660016A CN 2012100712420 A CN2012100712420 A CN 2012100712420A CN 201210071242 A CN201210071242 A CN 201210071242A CN 102660016 A CN102660016 A CN 102660016A
- Authority
- CN
- China
- Prior art keywords
- phenolphthalein
- terpolymer
- benzophenone
- dihalo
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides a 2,6-dihalo benzonitrile-4,4'dihalobenzophenone-phenolphthalein terpolymer which contains a first repeat unit as shown in formula (I) and a second repeat unit as shown in formula (II), wherein the mole ratio of the first repeat unit to the second repeat unit is 0.1:9.9 to 9.9:0.1. The invention further provides a preparation method of the 2,6-dihalobenzonitrile-4,4' dihalobenzophenone-phenolphthalein terpolymer, comprising the step of reacting 2,6-dihalo benzonitrile-4,4' dihalobenzophenone with phenolphthalein in an organic solvent in the presence of an alkali compound and a water-carrying agent to obtain the 2,6-dihalo benzonitrile-4,4' dihalobenzophenone-phenolphthalein terpolymer. The 2,6-dihalo benzonitrile-4,4' dihalobenzophenone-phenolphthalein terpolymer has good heat-resisting performance and can be used for preparing high-performance coatings, adhesives, functional membranes, high-performance composite materials and the like.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer and preparation method thereof.
Background technology
Polyaryletherketone (PEAK) is one type of polymkeric substance that the phenylene ring is formed by connecting through ehter bond and carbonyl, mainly contains kinds such as polyetheretherketone, polyetherketone, PEKK, polyether ether ketone ketone and polyetherketoneetherketoneketone at present.Polyaryletherketone is an analog thermoplastic high performance engineering plastics, has performances such as good thermotolerance, chemicalstability, antifatigue, radiation hardness, flame retardant resistance and dimensional stability, is widely used in fields such as electric, aerospace and automotive industry.For dissolving processing characteristics of improving above-mentioned traditional polyaryletherketone etc.; Application number is that 85108751 Chinese patent document discloses a kind of phenolphthalein polyaryletherketone; This product dissolves in N; Dinethylformamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), N-Methyl pyrrolidone (NMP) and haloalkane hydro carbons organic solvent, the dissolving processing characteristics is improved greatly, can be used as structured material such as film, sheet, plate, pipe and fiber and uses.
Poly (arylene ether nitrile) also is an analog thermoplastic high performance engineering plastics, it early than 1986 by the commercialization of the emerging product of Japanese bright dipping company, exploitation obtains the poly (arylene ether nitrile) product P AN of commodity ID300 by name.Comprise in the molecular structure of poly (arylene ether nitrile) strong polar cyanic acid (CN) side group, this has increased the effect of molecule interchain dipole-dipole on the one hand, not only is beneficial to obtain better heat-resisting performance and physical strength, and is beneficial to the sticking power that strengthens resin matrix; On the other hand; Cyanic acid can be used as a potential cross-linking set; Be beneficial to and form molecular network structure with higher resistance toheat; Therefore, poly (arylene ether nitrile) has advantages such as excellent mechanical property, resistance toheat and chemicalstability, in fields such as electronic apparatus manufacturing, aerospace and automotive industry, has broad application prospects; Equal to prepare a kind of phenolphthalein poly (arylene ether nitrile) in 1993 like Matsuo S, it has good comprehensive performances (Journal of Polymer Science.Part A; Polymer Chemistry 1993,31,3439).
The inventor considers, can cyanic acid be introduced in the molecular structure of phenolphthalein polyaryletherketone, further improves the second-order transition temperature of phenolphthalein polyaryletherketone etc., obtains better material such as resistance toheat, enlarges its range of application.
Summary of the invention
In view of this; The technical problem that the present invention will solve is to provide a kind of 2; 6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer and preparation method thereof, provided by the invention 2; 6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer has excellent heat resisting.
The invention provides a kind of 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer, have second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II):
The mol ratio of said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1.
It is a kind of 2 that the present invention also provides, 6-two halogen benzonitriles-4,4 '-preparation method of dihalo-benzophenone-phenolphthalein terpolymer, may further comprise the steps:
In the presence of basic cpd and band aqua, with 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone and phenolphthalein reacts in organic solvent, obtains 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.
Preferably, said 2,6-two halogen benzonitriles are 2,6-difluorobenzonitrile or 2, and the 6-dichlorobenzonitrile, said 4,4 '-the dihalo-benzophenone is 4,4 '-difluoro benzophenone or 4,4 '-two chloro benzophenones.
Preferably, said 2,6-two halogen benzonitriles and said 4; 4 '-mol ratio of dihalo-benzophenone is (0.05～0.95): (0.95～0.05); The amount of substance of said phenolphthalein and said 2,6-two halogen benzonitriles and said 4,4 '-ratio of total amount of substance of dihalo-benzophenone is (1～3): 1.
Preferably, said basic cpd is Anhydrous potassium carbonate, soda ash light, saleratus, sodium hydrogencarbonate, Pottasium Hydroxide or sodium hydroxide.
Preferably, the mol ratio of said basic cpd and said phenolphthalein is (1～3): 1.
Preferably, said organic solvent is tetramethylene sulfone, sulfobenzide or N-N-methyl 2-pyrrolidone N-, and said band aqua is YLENE or toluene.
Preferably, the volume ratio of said organic solvent and said band aqua is 1: (1～3).
Preferably, said preparation method is specially:
In the presence of basic cpd and band aqua, with 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone and phenolphthalein carries out the first step and reacts in organic solvent, obtain intermediate product;
Said intermediate product is carried out the reaction of second step, obtain 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.
Preferably, the temperature of said the first step reaction is 120 ℃～180 ℃, and the time of said the first step reaction is 2h～7h;
The temperature of said second step reaction is 180 ℃～240 ℃, and the time of said second step reaction is 3h～10h.
Compared with prior art, the present invention is with 2,6-two halogen benzonitriles, 4; 4 '-dihalo-benzophenone and phenolphthalein are raw material, in the presence of basic cpd and band aqua, in organic solvent, react, and obtain 2; 6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.Provided by the invention 2; 6-two halogen benzonitriles-4; 4 '-dihalo-benzophenone-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II), and the mol ratio of said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1.In the present invention; Said 2; Contain cyanic acid in the molecular structure of 6-two halogen benzonitriles-4,4 ' dihalo-benzophenone-phenolphthalein terpolymer, and the mol ratio that satisfies said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1; Have excellent heat resisting, can be used for preparing materials such as high-performance coating, tackiness agent, functional membrane and high performance composite.Experimental result shows, and is provided by the invention 2,6-two halogen benzonitriles-4; 4 '-dihalo-benzophenone-phenolphthalein terpolymer is a flocculent substance; Have second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II), its limiting viscosity >=0.2dL/g, second-order transition temperature are 225 ℃～265 ℃; The temperature of initial weightlessness is 340 ℃～385 ℃, and weightless 5% temperature is 400 ℃～490 ℃.
In addition, provided by the invention 2,6-two halogen benzonitriles-4,4 '-preparation method of dihalo-benzophenone-phenolphthalein terpolymer implements easily, is easy to apply.
Description of drawings
Fig. 1 obtain for the embodiment of the invention 12, the infrared spectrogram of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer;
Fig. 2 obtain for the embodiment of the invention 12, the carbon-13 nmr spectra figure of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer;
Fig. 3 obtain for the embodiment of the invention 12, the hydrogen nuclear magnetic resonance spectrogram of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer.
Embodiment
The invention provides a kind of 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer, have second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II):
The mol ratio of said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1.
Provided by the invention 2; 6-two halogen benzonitriles-4; 4 '-comprise strong polar cyanic acid in the molecular structure of dihalo-benzophenone-phenolphthalein terpolymer, increased the effect of phenolphthalein polyaryletherketone molecule interchain dipole-dipole, be beneficial to the resistance toheat that improves the phenolphthalein polyaryletherketone etc.
In the present invention, the mol ratio of said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1, is preferably 0.5: 9.5～9.5: 0.5, more preferably 1: 9～9: 1.Experimental result shows; The mol ratio that satisfies said first repeating unit and said second repeating unit be 0.1: 9.9～9.9: 0.1 2; 6-two halogen benzonitriles-4; 4 '-Good Heat-resistance of dihalo-benzophenone-phenolphthalein terpolymer, can be used for preparing materials such as high-performance coating, tackiness agent, functional membrane and high performance composite.
The present invention does not have particular restriction to the polymerization degree of said first repeating unit and said second repeating unit; The polymerization degree of said first repeating unit is preferably 1～500; More preferably 2～200, most preferably be 3～100, the polymerization degree of said second repeating unit is preferably 1～500; More preferably 2～200, most preferably be 3～100.
In the present invention, said 2,6-two halogen benzonitriles-4,4 '-limiting viscosity ([η]) >=0.2dL/g of dihalo-benzophenone-phenolphthalein terpolymer;
Said 2,6-two halogen benzonitriles-4,4 '-second-order transition temperature of dihalo-benzophenone-phenolphthalein terpolymer is 225 ℃～265 ℃;
Said 2,6-two halogen benzonitriles-4,4 '-temperature of the initial weightlessness of dihalo-benzophenone-phenolphthalein terpolymer is 340 ℃～385 ℃, weightless 5% temperature is 400 ℃～490 ℃.
It is a kind of 2 that the present invention also provides, 6-two halogen benzonitriles-4,4 '-preparation method of dihalo-benzophenone-phenolphthalein terpolymer, may further comprise the steps:
In the presence of basic cpd and band aqua, with 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone and phenolphthalein reacts in organic solvent, obtains 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.
The present invention is 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone, phenolphthalein, basic cpd, band aqua and organic solvent place reactor drum to heat, and obtains 2 after the reaction, 6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.
The present invention preferably under rare gas element such as nitrogen protection, with 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone and phenolphthalein are raw material, reaction obtains 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.The present invention introduces cyanic acid in the molecular structure of phenolphthalein polyaryletherketone through above-mentioned raw materials generation nucleophilic substitution reaction and polycondensation, has improved the resistance toheat of phenolphthalein polyaryletherketone, has enlarged range of application.
In addition, the above-mentioned raw materials wide material sources that the present invention is used, cost is lower, and the ratio of performance to price is higher, has favorable economic benefit and social benefit.
In the present invention, said 2,6-two halogen benzonitriles are preferably 2,6-difluorobenzonitrile or 2,6-dichlorobenzonitrile, more preferably 2,6-dichlorobenzonitrile; Said 4,4 '-the dihalo-benzophenone is preferably 4,4 '-difluoro benzophenone or 4,4 '-two chloro benzophenones, more preferably 4,4 '-two chloro benzophenones;
Said 2,6-two halogen benzonitriles and said 4,4 '-mol ratio of dihalo-benzophenone is preferably (0.05～0.95): (0.95～0.05), more preferably (0.1～0.9): (0.9～0.1); The amount of substance of said phenolphthalein and said 2,6-two halogen benzonitriles and said 4,4 '-ratio of total amount of substance of dihalo-benzophenone is preferably (1～3): 1, more preferably (1～2.5): 1, most preferably be 1: 1.Said 2 through regulating, 6-two halogen benzonitriles, said 4,4 '-ratio of dihalo-benzophenone and said phenolphthalein, can obtain the polymer product of different cyanic acid content, show the structure and the performance that can require the controlling polymers product according to molecular designing.
In the present invention; Said basic cpd can play katalysis to reaction; Said basic cpd is preferably Anhydrous potassium carbonate, soda ash light, saleratus, sodium hydrogencarbonate, Pottasium Hydroxide or sodium hydroxide; More preferably Anhydrous potassium carbonate or soda ash light most preferably are Anhydrous potassium carbonate; The mol ratio of said basic cpd and said phenolphthalein is preferably (1～3): 1, more preferably (1.1～2.5): 1, most preferably be (1.15～2): 1;
Said organic solvent is the medium of reaction, and said organic solvent is preferably tetramethylene sulfone, sulfobenzide or N-N-methyl 2-pyrrolidone N-, more preferably tetramethylene sulfone; The present invention does not have particular restriction to the consumption of said organic solvent, adopts the consoluet consumption of above-mentioned raw materials is got final product;
Said band aqua can be separated the water that reaction produces from reaction system, thereby improves reaction efficiency, and said band aqua is preferably YLENE or toluene, more preferably YLENE; The volume ratio of said organic solvent and said band aqua is preferably 1: (1～3), more preferably 1: (1.5～2.5) most preferably are 1: (1.8～2).
In the present invention, said 2,6-two halogen benzonitriles-4,4 '-preparation method of dihalo-benzophenone-phenolphthalein terpolymer preferably is specially:
In the presence of basic cpd and band aqua, with 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone and phenolphthalein carries out the first step and reacts in organic solvent, obtain intermediate product;
Said intermediate product is carried out the reaction of second step, obtain 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.
Wherein, said the first step reaction is main with nucleophilic substitution reaction, and the temperature of said the first step reaction is preferably 120 ℃～180 ℃, more preferably 130 ℃～170 ℃, most preferably is 140 ℃～160 ℃; The time of said the first step reaction is preferably 2h～7h, and more preferably 3h～6h most preferably is 4h～5h;
Said band aqua is taken the water that reaction produces out of, and the present invention obtains intermediate product after preferably steaming whole said band aquas, and said intermediate product comprises product and the small amounts of oligomer of nucleophilic substitution reaction etc.;
Said second step reaction is main with polycondensation, and the temperature of said second step reaction is preferably 180 ℃～240 ℃, more preferably 200 ℃～220 ℃; The time of said second step reaction is preferably 3h～10h, and more preferably 4h～9h most preferably is 5h～8h.
When reaction obtained thick polymer product, the present invention added the cooling of the reaction system in the reactor drum N,N-DIMETHYLACETAMIDE (DMAC) and dilutes; Under vigorous stirring, precipitate in the impouring ethanol then, boil repeatedly with zero(ppm) water again after the filtration and wash polymer product, to remove residual basic cpd etc.; Polymer product after will filtering at last is dry, obtains cotton-shaped product 2,6-two halogen benzonitriles-4; 4 '-dihalo-benzophenone-phenolphthalein terpolymer, calculate productive rate greater than 90%.
After obtaining said cotton-shaped product, it is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy.Analytical results shows, and is said 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
With said 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer is dissolved in N, in the dinethylformamide (DMF), under 25 ℃ temperature, measures its limiting viscosity.Mensuration result shows, and is said 2,6-two halogen benzonitriles-4,4 '-limiting viscosity >=0.2dL/g of dihalo-benzophenone-phenolphthalein terpolymer.
Utilize METTLER TOLEDO DSC1 DSC to measure said 2; 6-halogen benzonitrile-4; 4 '-second-order transition temperature of dihalo-benzophenone-phenolphthalein terpolymer; Condition determination is following: under nitrogen protection, heat-up rate is 10 ℃/min, and the TR of mensuration is 0 ℃～300 ℃.Mensuration result shows, and is said 2,6-halogen benzonitrile-4,4 '-second-order transition temperature of dihalo-benzophenone-phenolphthalein terpolymer is 225 ℃～265 ℃.
Utilize METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer to measure said 2; 6-halogen benzonitrile-4,4 '-thermal decomposition performance of dihalo-benzophenone-phenolphthalein terpolymer, condition determination is following: under nitrogen protection; Heat-up rate is 10 ℃/min, and the TR of mensuration is 0 ℃～600 ℃.Mensuration result shows, and is said 2,6-halogen benzonitrile-4,4 '-temperature of the initial weightlessness of dihalo-benzophenone-phenolphthalein terpolymer is 340 ℃～385 ℃, weightless 5% temperature is 400 ℃～490 ℃.
Experimental result shows; Provided by the invention 2; 6-halogen benzonitrile-4; 4 '-dihalo-benzophenone-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II), and the mol ratio of said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1; Said 2,6-halogen benzonitrile-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer has excellent heat resisting, can be used for preparing materials such as high-performance coating, tackiness agent, functional membrane and high performance composite.
In addition, preparation method provided by the invention implements easily, is easy to apply.
In order to further specify the present invention, below in conjunction with embodiment to provided by the invention 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer and preparation method thereof describes in detail.
Embodiment 1
With 10mmol phenolphthalein, 3mmol4; 4 '-two chloro benzophenones, 7mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 120 ℃ of constant temperature azeotropic band water reactions, behind the 7h YLENE all steamed;
Be heated to 180 ℃ then and continue reaction, behind the reaction 10h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-chlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 90%.
Said cotton-shaped product is carried out IR spectroscopy, and analytical results is referring to Fig. 1, Fig. 1 obtain for the embodiment of the invention 12, the infrared spectrogram of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer.Can know wave number 3516cm by Fig. 1
-1The place is terminal phenolphthalein hydroxyl vibration peak, wave number 3042cm
-1The place is C-H stretching vibration peak on the phenyl ring, wave number 2230cm
-1The place is-CN stretching vibration peak, i.e. the charateristic avsorption band of cyanic acid, wave number 1772cm
-1The place is the carbonylic stretching vibration peak on the phenolphthalein structure unit lactone, wave number 1653cm
-1The place is benzophenone carbonylic stretching vibration peak, wave number 1593cm
-1, wave number 1501cm
-1, wave number 1460cm
-1With wave number 1411cm
-1The place is phenyl ring skeleton stretching vibration peak, wave number 1243cm
-1The place is C-O-C stretching vibration peak on the aryl oxide, i.e. the characteristic peak of aryl oxide, wave number 1162cm
-1The place is C-O stretching vibration peak in the phenolphthalein lactone, wave number 1101cm
-1, wave number 1080cm
-1, wave number 1016cm
-1And 971cm
-1The place is phenyl ring in-plane bending vibration peak, wave number 839cm
-1The place replaces characteristic peak, wave number 754cm for phenyl ring is two
-1With wave number 690cm
-1The place is out-of-plane bending vibration peak on the phenyl ring.
Said cotton-shaped product is carried out nuclear magnetic resonance spectroscopy; Analytical results is referring to Fig. 2 and Fig. 3, Fig. 2 obtain for the embodiment of the invention 12,6-dichlorobenzonitrile-4; The carbon-13 nmr spectra figure of 4 '-two chloro benzophenones-phenolphthalein terpolymer; Fig. 3 obtain for the embodiment of the invention 12, the hydrogen nuclear magnetic resonance spectrogram of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer.Can know by Fig. 2; 193.08ppm the peak of chemical shift place belongs to 11 carbonyl carbon on the benzophenone; 168.55ppm the peak of chemical shift place belongs to 8 carbonyl carbon on the phenolphthalein lactonic ring, the peak of 159.99ppm chemical shift place belongs on the benzophenone phenyl ring 19 carbon, and the peak of 159.63ppm chemical shift place belongs on the benzene nitrile phenyl ring 14 carbon; 155.50ppm, the peak of 154.89ppm chemical shift place belongs on the phenolphthalein phenyl ring 1 carbon; 151.29ppm the peak of chemical shift place belongs on the phenolphthalein phenyl ring 6 carbon, the peak of 137.16ppm, 136.42ppm chemical shift place belongs on the phenolphthalein phenyl ring 5 carbon, and the peak of 135.94ppm chemical shift place belongs on the benzophenone phenyl ring 22 carbon; 135.22ppm the peak of chemical shift place belongs on the benzophenone phenyl ring 10 carbon; 132.09ppm the peak of chemical shift place belongs on the benzophenone phenyl ring 21 carbon, the peak of 131.06ppm chemical shift place belongs on the benzene nitrile phenyl ring 16 carbon, and the peak of 130.10ppm chemical shift place belongs on the phenolphthalein phenyl ring 12 carbon; 128.90ppm the peak of chemical shift place belongs on the phenolphthalein phenyl ring 3 carbon; 126.01ppm the peak of chemical shift place belongs on the phenolphthalein phenyl ring 7 carbon, the peak of 124.54ppm chemical shift place belongs on the phenolphthalein phenyl ring 9 carbon, and the peak of 124.26ppm chemical shift place belongs on the phenolphthalein phenyl ring 13 carbon; 119.67ppm the peak of chemical shift place belongs on the phenolphthalein phenyl ring 2 carbon; 117.71ppm the peak of chemical shift place belongs on the benzophenone phenyl ring 20 carbon, the peak of 112.68ppm chemical shift place belongs to the carbon of 18 in cyanic acid on the benzene nitrile, and the peak of 112.14ppm chemical shift place belongs on the benzene nitrile phenyl ring 15 carbon; 95.29ppm the peak of chemical shift place belongs on the benzene nitrile phenyl ring 17 carbon, the peak of 90.17ppm chemical shift place belongs on the phenolphthalein 4 carbon;
Can know by Fig. 3; 7.97ppm the peak of chemical shift place belongs on the phenolphthalein phenyl ring 6 hydrogen; 7.90ppm the peak of chemical shift place belongs on the phenolphthalein phenyl ring 4 hydrogen, the peak of 7.76ppm chemical shift place belongs on the phenolphthalein phenyl ring 5 hydrogen, and the peak of 7.72ppm chemical shift place belongs on the phenolphthalein phenyl ring 3 hydrogen; 7.54ppm the peak of chemical shift place belongs on the benzene nitrile phenyl ring 8 hydrogen; 7.45ppm the peak of chemical shift place belongs on the phenolphthalein phenyl ring 1 hydrogen, the peak of 7.25ppm chemical shift place belongs on the phenolphthalein phenyl ring 2 hydrogen, and the peak of 7.17ppm chemical shift place belongs on the benzophenone phenyl ring 10 hydrogen; 7.14ppm the peak of chemical shift place belongs on the benzophenone phenyl ring 9 hydrogen, the peak of 6.72ppm chemical shift place belongs on the benzene nitrile phenyl ring 7 hydrogen.
In sum, said 2,6-chlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-chlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.34dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 243 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 350 ℃, and weightless 5% temperature is 427 ℃.
Embodiment 2
With 10mmol phenolphthalein, 5mmol4; 4 '-two chloro benzophenones, 5mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 150 ℃ of constant temperature azeotropic band water reactions, behind the 5h YLENE all steamed;
Be heated to 240 ℃ then and continue reaction, behind the reaction 6h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-chlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 95%.
Said cotton-shaped product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy; Analytical results shows; Said 2,6-chlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.45dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 243 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 340 ℃, and weightless 5% temperature is 424 ℃.
Embodiment 3
With 10mmol phenolphthalein, 2mmol4; 4 '-two chloro benzophenones, 8mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 120 ℃ of constant temperature azeotropic band water reactions, behind the 7h YLENE all steamed;
Be heated to 220 ℃ then and continue reaction, behind the reaction 6h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 92%.
Said cotton-shaped product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy; Analytical results shows; Said 2,6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.63dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 250 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 345 ℃, and weightless 5% temperature is 430 ℃.
With 10mmol phenolphthalein, 1mmol4; 4 '-two chloro benzophenones, 9mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 140 ℃ of constant temperature azeotropic band water reactions, behind the 5h YLENE all steamed;
Be heated to 180 ℃ then and continue reaction, behind the reaction 10h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 93%.
Said cotton-shaped product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy; Analytical results shows; Said 2,6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.28dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 251 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 350 ℃, and weightless 5% temperature is 425 ℃.
With 10mmol phenolphthalein, 0.5mmol4; 4 '-two chloro benzophenones, 9.5mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 150 ℃ of constant temperature azeotropic band water reactions, behind the 5h YLENE all steamed;
Be heated to 210 ℃ then and continue reaction, behind the reaction 6h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 92%.
Said cotton-shaped product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy; Analytical results shows; Said 2,6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.49dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 256 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 360 ℃, and weightless 5% temperature is 436 ℃.
Embodiment 6
With 10mmol phenolphthalein, 9.5mmol4; 4 '-two chloro benzophenones, 0.5mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 170 ℃ of constant temperature azeotropic band water reactions, behind the 5h YLENE all steamed;
Be heated to 220 ℃ then and continue reaction, behind the reaction 6h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 92%.
Said cotton-shaped product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy; Analytical results shows; Said 2,6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.54dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 225 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 350 ℃, and weightless 5% temperature is 445 ℃.
Embodiment 7
With 10mmol phenolphthalein, 8mmol4; 4 '-two chloro benzophenones, 2mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 170 ℃ of constant temperature azeotropic band water reactions, behind the 5h YLENE all steamed;
Be heated to 260 ℃ then and continue reaction, behind the reaction 5h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 93%.
Said cotton-shaped product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy; Analytical results shows; Said 2,6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.53dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 229 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 360 ℃, and weightless 5% temperature is 445 ℃.
Embodiment 8
With 10mmol phenolphthalein, 7mmol4; 4 '-two chloro benzophenones, 3mmol2; 6-dichlorobenzonitrile, 11.5mmol Anhydrous potassium carbonate, 10mL tetramethylene sulfone and 20mL YLENE place the flask that has water trap, TM, mechanical stirrer and logical nitrogen tube; Be heated to 160 ℃ of constant temperature azeotropic band water reactions, behind the 5h YLENE all steamed;
Be heated to 250 ℃ then and continue reaction, behind the reaction 6h, obtain thick polymer product, stop heating; Cooling back adds 20mLDMAC, stir, under vigorous stirring with precipitating in its impouring ethanol; Boil repeatedly with zero(ppm) water again after the filtration and wash polymer product,, obtain cotton-shaped product 2 through dry; 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer, productive rate is greater than 90%.
Said cotton-shaped product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy; Analytical results shows; Said 2,6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II).
Measure saidly 2 according to measuring method mentioned above, the limiting viscosity of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its limiting viscosity is 0.60dL/g.
Measure saidly 2 according to measuring method mentioned above, the second-order transition temperature of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that its second-order transition temperature is 234 ℃.
Measure saidly 2 according to measuring method mentioned above, the thermal decomposition performance of 6-dichlorobenzonitrile-4,4 '-two chloro benzophenones-phenolphthalein terpolymer is measured the result and is shown that the temperature of its initial weightlessness is 360 ℃, and weightless 5% temperature is 460 ℃.
Can know by above embodiment; Provided by the invention 2; 6-two halogen benzonitriles-4; 4 '-dihalo-benzophenone-phenolphthalein terpolymer is a flocculent substance, has second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II), the mol ratio of said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1.Said 2,6-two halogen benzonitriles-4,4 '-limiting viscosity >=0.2dL/g of dihalo-benzophenone-phenolphthalein terpolymer, second-order transition temperature is 225 ℃～265 ℃, and the temperature of initial weightlessness is 340 ℃～385 ℃, and weightless 5% temperature is 400 ℃～490 ℃.
Experimental result shows, and is provided by the invention 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer has excellent heat resisting, can be used for preparing materials such as high-performance coating, tackiness agent, functional membrane and high performance composite.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1.2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer, have second repeating unit shown in first repeating unit shown in the formula (I) and the formula (II):
The mol ratio of said first repeating unit and said second repeating unit is 0.1: 9.9～9.9: 0.1.
6-two halogen benzonitriles-4,4 '-preparation method of dihalo-benzophenone-phenolphthalein terpolymer, may further comprise the steps:
In the presence of basic cpd and band aqua, with 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone and phenolphthalein reacts in organic solvent, obtains 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.
3. preparation method according to claim 2 is characterized in that, and is said 2, and 6-two halogen benzonitriles are 2,6-difluorobenzonitrile or 2, and the 6-dichlorobenzonitrile, said 4,4 '-the dihalo-benzophenone is 4,4 '-difluoro benzophenone or 4,4 '-two chloro benzophenones.
4. preparation method according to claim 2; It is characterized in that, said 2,6-two halogen benzonitriles and said 4; 4 '-mol ratio of dihalo-benzophenone is (0.05～0.95): (0.95～0.05); The amount of substance of said phenolphthalein and said 2,6-two halogen benzonitriles and said 4,4 '-ratio of total amount of substance of dihalo-benzophenone is (1～3): 1.
5. preparation method according to claim 2 is characterized in that, said basic cpd is Anhydrous potassium carbonate, soda ash light, saleratus, sodium hydrogencarbonate, Pottasium Hydroxide or sodium hydroxide.
6. preparation method according to claim 2 is characterized in that, the mol ratio of said basic cpd and said phenolphthalein is (1～3): 1.
7. preparation method according to claim 2 is characterized in that, said organic solvent is tetramethylene sulfone, sulfobenzide or N-N-methyl 2-pyrrolidone N-, and said band aqua is YLENE or toluene.
8. preparation method according to claim 2 is characterized in that, the volume ratio of said organic solvent and said band aqua is 1: (1～3).
9. preparation method according to claim 2 is characterized in that, said preparation method is specially:
In the presence of basic cpd and band aqua, with 2,6-two halogen benzonitriles, 4,4 '-dihalo-benzophenone and phenolphthalein carries out the first step and reacts in organic solvent, obtain intermediate product;
Said intermediate product is carried out the reaction of second step, obtain 2,6-two halogen benzonitriles-4,4 '-dihalo-benzophenone-phenolphthalein terpolymer.
10. preparation method according to claim 9 is characterized in that, the temperature of said the first step reaction is 120 ℃～180 ℃, and the time of said the first step reaction is 2h～7h;
The temperature of said second step reaction is 180 ℃～240 ℃, and the time of said second step reaction is 3h～10h.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210071242.0A CN102660016B (en) | 2012-03-16 | 2012-03-16 | 2,6-dihalo benzonitrile-4,4'dihalobenzophenone-phenolphthalein terpolymer and preparation method thereof |
| PCT/CN2013/071654 WO2013135127A1 (en) | 2012-03-16 | 2013-02-19 | 2,6-dihalobenzonitrile-4,4'-dihalobenzophenone-phenolphthalein terpolymer, preparation method thereof and insulating coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210071242.0A CN102660016B (en) | 2012-03-16 | 2012-03-16 | 2,6-dihalo benzonitrile-4,4'dihalobenzophenone-phenolphthalein terpolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102660016A true CN102660016A (en) | 2012-09-12 |
| CN102660016B CN102660016B (en) | 2014-12-10 |
Family
ID=46769612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210071242.0A Active CN102660016B (en) | 2012-03-16 | 2012-03-16 | 2,6-dihalo benzonitrile-4,4'dihalobenzophenone-phenolphthalein terpolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102660016B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013135127A1 (en) * | 2012-03-16 | 2013-09-19 | 中国科学院长春应用化学研究所 | 2,6-dihalobenzonitrile-4,4'-dihalobenzophenone-phenolphthalein terpolymer, preparation method thereof and insulating coating composition |
| CN107474242A (en) * | 2017-09-06 | 2017-12-15 | 中国科学院长春应用化学研究所 | A kind of polymer containing long branched chain structure, preparation method and foamed material |
| CN113004512A (en) * | 2019-12-20 | 2021-06-22 | 中国科学院大连化学物理研究所 | Polymer and preparation method and application thereof |
| CN114687213A (en) * | 2022-04-26 | 2022-07-01 | 浙江大学衢州研究院 | Crosslinkable polyarylether nitrile aqueous sizing agent and preparation method and application thereof |
| CN114687213B (en) * | 2022-04-26 | 2024-05-10 | 浙江大学衢州研究院 | Cross-linkable poly (arylene ether nitrile) aqueous sizing agent and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108751A (en) * | 1985-11-25 | 1987-06-03 | 中国科学院长春应用化学研究所 | The synthetic novel polyether ether ketone that has the phthalein side group |
| EP0373633A2 (en) * | 1988-12-14 | 1990-06-20 | Idemitsu Kosan Company Limited | Polyetheric copolymers, process for preparing the same, compositions containing the same, their molded products, and their use |
| CN1124745A (en) * | 1994-12-13 | 1996-06-19 | 四川联合大学 | Polyaryl ether nitrile and producing process thereof |
| CN1238347A (en) * | 1998-06-05 | 1999-12-15 | 四川联合大学 | Polyaryl ether-nitrile-sulfone containing phenolphthalein structure and its preparing process |
| CN101838390A (en) * | 2010-05-28 | 2010-09-22 | 电子科技大学 | Method for preparing poly(arylene ether nitrile) resin |
| CN101948568A (en) * | 2010-09-16 | 2011-01-19 | 电子科技大学 | Method for preparing poly(arylene ether nitrile) resin powder |
-
2012
- 2012-03-16 CN CN201210071242.0A patent/CN102660016B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108751A (en) * | 1985-11-25 | 1987-06-03 | 中国科学院长春应用化学研究所 | The synthetic novel polyether ether ketone that has the phthalein side group |
| EP0373633A2 (en) * | 1988-12-14 | 1990-06-20 | Idemitsu Kosan Company Limited | Polyetheric copolymers, process for preparing the same, compositions containing the same, their molded products, and their use |
| CN1124745A (en) * | 1994-12-13 | 1996-06-19 | 四川联合大学 | Polyaryl ether nitrile and producing process thereof |
| CN1238347A (en) * | 1998-06-05 | 1999-12-15 | 四川联合大学 | Polyaryl ether-nitrile-sulfone containing phenolphthalein structure and its preparing process |
| CN101838390A (en) * | 2010-05-28 | 2010-09-22 | 电子科技大学 | Method for preparing poly(arylene ether nitrile) resin |
| CN101948568A (en) * | 2010-09-16 | 2011-01-19 | 电子科技大学 | Method for preparing poly(arylene ether nitrile) resin powder |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013135127A1 (en) * | 2012-03-16 | 2013-09-19 | 中国科学院长春应用化学研究所 | 2,6-dihalobenzonitrile-4,4'-dihalobenzophenone-phenolphthalein terpolymer, preparation method thereof and insulating coating composition |
| CN107474242A (en) * | 2017-09-06 | 2017-12-15 | 中国科学院长春应用化学研究所 | A kind of polymer containing long branched chain structure, preparation method and foamed material |
| CN107474242B (en) * | 2017-09-06 | 2019-04-02 | 中国科学院长春应用化学研究所 | A kind of polymer containing long branched chain structure, preparation method and foamed material |
| CN113004512A (en) * | 2019-12-20 | 2021-06-22 | 中国科学院大连化学物理研究所 | Polymer and preparation method and application thereof |
| CN113004512B (en) * | 2019-12-20 | 2021-11-02 | 中国科学院大连化学物理研究所 | Polymer and preparation method and application thereof |
| CN114687213A (en) * | 2022-04-26 | 2022-07-01 | 浙江大学衢州研究院 | Crosslinkable polyarylether nitrile aqueous sizing agent and preparation method and application thereof |
| CN114687213B (en) * | 2022-04-26 | 2024-05-10 | 浙江大学衢州研究院 | Cross-linkable poly (arylene ether nitrile) aqueous sizing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102660016B (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chuang et al. | Synthesis and properties of a new fluorine‐containing polybenzimidazole for high‐temperature fuel‐cell applications | |
| Yang et al. | Strengthening phosphoric acid doped polybenzimidazole membranes with siloxane networks for using as high temperature proton exchange membranes | |
| CN101704989B (en) | Fluorine-containing imine matrix resin used for advanced composite material and preparation method thereof | |
| CN101619131A (en) | O-phthalodinitrile end-blocked soluble polyarylether resin with phthalazinone structure and condensate and preparation method thereof | |
| Zhao et al. | A high temperature polymer of phthalonitrile‐substituted phosphazene with low melting point and good thermal stability | |
| CN104311756B (en) | Silicone containing bismaleimide resin and its preparation | |
| CN103450478B (en) | A kind of polyaryletherketone and preparation method thereof | |
| Liu et al. | Fluorinated poly (aryl ether) containing a 4‐bromophenyl pendant group and its phosphonated derivative | |
| Ma et al. | Poly (aryl ether ketone) s with bromomethyl groups: Synthesis and quaternary amination | |
| CN101186695A (en) | Soluble fluorine-containing polyaryl ether ketone high-performance material, preparation method thereof and mixed film of the same and epoxy resin | |
| CN102660016B (en) | 2,6-dihalo benzonitrile-4,4'dihalobenzophenone-phenolphthalein terpolymer and preparation method thereof | |
| CN101775138B (en) | Novel polytriazoles imide resin and preparation method thereof | |
| CN104130409A (en) | Preparation method of phenolphthalein polyimide | |
| Xu et al. | Synthesis of novel polybenzimidazoles with pendant amino groups and the formation of their crosslinked membranes for medium temperature fuel cell applications | |
| CN101774973A (en) | Polyamine containing triazole ring and preparation method and application thereof | |
| CN102875800B (en) | Phenolphthalein polyarylether ketone copolymer and preparation method thereof | |
| CN102887999A (en) | Bisphenol A bisphthalonitrile resin containing arylethernitrile chain segment, cured resin and preparation method thereof | |
| Akbarian‐Feizi et al. | Synthesis of new sulfonated copolyimides in organic and ionic liquid media for fuel cell application | |
| CN103319715B (en) | Hydrolysis-resistanteasy-processable easy-processable polythioetherimide resin material and preparation method thereof | |
| CN103204991B (en) | Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone | |
| CN102127224B (en) | Modified cyanate resin and preparation method thereof | |
| CN102585210A (en) | Phenolphthalein polyaryletherketone and preparation method thereof | |
| CN102432436A (en) | Poly-fluorophenyl-substituted aromatic diphenol and synthesis method and application thereof | |
| CN101591436B (en) | Polybenzimidazole containing diazanaphthalene terphenyl structure and preparation method thereof | |
| CN102492132A (en) | Polyaryletherketone copolymers containing cyano group and preparation method for polyaryletherketone copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180814 Address after: 130012 5218 Longhu Road, north new hi-tech, Changchun, Jilin Patentee after: Changchun applied chemical science and Technology General Corporation of Chinese Academy of Sciences Address before: No. 5625, people's street, Changchun, Jilin Province, Jilin Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180906 Address after: 132000 room 306, 480 Jilu Road, Jilin economic and Technological Development Zone, Jilin, Jilin Patentee after: Jilin Zhongke Polymerization Technology Co., Ltd. Address before: 130012 5218 Longhu Road, north new hi-tech, Changchun, Jilin Patentee before: Changchun applied chemical science and Technology General Corporation of Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right |