CN1197894C - Polyarylether-nitrile-sulphone contg. diazanaphthaleneone biphenyl structure and preparing process thereof - Google Patents
Polyarylether-nitrile-sulphone contg. diazanaphthaleneone biphenyl structure and preparing process thereof Download PDFInfo
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- CN1197894C CN1197894C CN 03111541 CN03111541A CN1197894C CN 1197894 C CN1197894 C CN 1197894C CN 03111541 CN03111541 CN 03111541 CN 03111541 A CN03111541 A CN 03111541A CN 1197894 C CN1197894 C CN 1197894C
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Abstract
The present invention discloses polyarylether nitrile sulphone with naphthyridine ketone biphenyl structure and a method for preparing the polyarylether nitrile sulphone, which belongs to the technical field of high molecular material science. The present invention is characterized in that structural units shown in the formula I are contained on macro molecule main chains. Used monomers are dihalogenated cyanobenzene (the halogen can be fluorine and chlorine), novel bisphenol with naphthyridine ketone biphenyl structure, and dihalogenated diphenyl sulfone. In reaction, salts of alkaline metal or alkaline earth metal are used as catalysts, and the present invention is obtained in non-protonic polar solvent through high temperature polymerization. The polymer has the characteristics of high molecular weight (the inherent viscosity is from 0.2 to 1.0 dl/g), high temperature resistance (the glass transition temperature is from 300 to 250 DEG C), favorable toughness, high intensity, favorable electrical property, a plurality of processing methods, wide application prospect, etc.
Description
Technical field
The invention belongs to the polymer material science technical field, relate to the high performance engineering plastics synthetic technology, specially refer to a kind of phthalazine biphenyl structure polyaryl ether-nitrile-sulfone and preparation method thereof of containing.
Background technology
Poly (arylene ether nitrile) is the novel polyarylether class of the class high performance engineering plastics of succeeding in developing in recent years.The European patent EP 0192177 and [the Journal of Polymer Science.Part A of application such as the Japanese S.Matsuo of Idemitsu Kosen Co., Ltd. in 1986; PolymerChemistry 31,3439 (1993)] in the synthetic technology of a series of poly (arylene ether nitrile)s is disclosed.China ZLCN1124754A and CN1238347A also disclose the synthetic technology of two kinds of novel polyaryl ether-nitrile-sulfones.
Chinese invention patent ZL93109180.2 and ZL93109179.9 disclose several novel fire resistant polyarylether resins, relate to the synthetic and use of the novel class biphenol monomer of phthalazone.
Foregoing invention does not all relate to the study on the synthesis of the novel polyaryl ether-nitrile-sulfone that contains phthalazine biphenyl structure.In poly (arylene ether nitrile) macromolecular main chain structure, introduce aryl ether sulfone and phthalazine biphenyl structure, given poly (arylene ether nitrile) a lot of properties, thermotolerance, toughness, the mechanical property of polymkeric substance had both been increased, make it have solvability preferably again, can widen application in fields such as film, separatory membrane, coating, insullac.Relevant patented technology report is not seen in the research of the polyaryl ether-nitrile-sulfone of relevant this excellent combination property, does not at home and abroad occur in the public publication yet.
Summary of the invention
The objective of the invention is from Molecular Structure Design, a kind of novel polyaryl ether-nitrile-sulfone that contains phthalazine biphenyl structure is provided, its second-order transition temperature is 300-350 ℃, can be dissolved in chloroform, N-Methyl pyrrolidone (NMP), N, N-N,N-DIMETHYLACETAMIDE minority polar solvents such as (DMAC) is to satisfy the higher level demands of applications.
Technical scheme of the present invention is the new monomer of diazanaphthalene terphenyl phenol (DHPZ) produced according to Chinese patent ZL93109180.2 with DaLian BaoLiMo New Materials Co., Ltd and commercially available 2,6-two halobenzene nitriles and activatory fragrance dihalo-sulfobenzide monomer are raw material, salt with basic metal or alkaline-earth metal is a catalyzer, makes the polyaryl ether-nitrile-sulfone performance resins that contains phthalazine biphenyl structure through solution nucleophilic substitution step-reaction polymerization.
Effect of the present invention and benefit have been to provide the novel polyarylether high-performance polymer that contains phthalazine biphenyl structure and itrile group side group in a kind of molecular chain simultaneously, excellent combination property, not only high temperature resistant but also solubilized, but also the activity that can utilize its itrile group is carried out functional modification or controlled crosslinked, satisfies multiple special purpose requirement.
Embodiment
Concrete synthetic method of the present invention is to contain the class biphenol monomer of phthalazine biphenyl structure, 2,6-two halobenzene nitriles and dihalo-sulfobenzide are raw material, in polar solvent, be catalyzer with the salt of basic metal or alkaline-earth metal, at high temperature carry out polymerization, carry out azeotropic dehydration in the reaction, after reaction finishes, stir down polymer precipitation to be come out, separate, clean, drying obtains polymkeric substance with precipitation agent.
It is characterized in that containing in this polymer molecular chain following structural unit:
R1, R2, R3, R4 can be alkyl, phenyl, hydrogen atom or halogen atom in the formula.
The class biphenol monomer that the present invention adopts contains phthalazine biphenyl structure, also claims diazanaphthalene terphenyl phenol (DHPZ) monomer.Its general structure is:
R1, R2, R3, R4 can be alkyl, phenyl, hydrogen atom or halogen atom in the formula.
Two halogen monomers that the present invention adopts are 2, and 6-two halobenzene nitriles, dihalo-sulfobenzide perhaps add dihalo-benzophenone or dihalo-pair again and make the co-polymer that contains carbonyl in this polymerization system.
Polymeric reaction temperature of the present invention is controlled at 120-240 ℃, and polymerization reaction time is 5-40 hour.The polyreaction formula can be expressed as follows:
R: alkyl, phenyl, hydrogen atom or halogen atom
X：F，Cl
Polymerization process can be divided into two stages.Fs is the pre-polymerization water smoking, adopts the entrainer azeotropic dehydration.This stage mainly generates oligopolymer, and system viscosity changes less, has big water gaging to be deviate from.To be with the water entrainer to steam, reaction enters subordinate phase.Subordinate phase mainly is to react between the oligopolymer, generates superpolymer, and system viscosity progressively increases.Treat that viscosity enlarges markedly, reach after the requirement, stop heating, cool, or add the end-capping reagent termination reaction.After reaction finishes, stir down with precipitation agent, separate, clean, dry polymkeric substance cohesion, precipitation, the poly (arylene ether nitrile) sulphone resin of white light yellow complexion.
The structure of polymkeric substance is confirmed through analytical procedures such as infrared spectra and nucleus magnetic resonance.With the chloroform is the limiting viscosity that solvent is measured polymkeric substance, and by changing monomer ratio and polymerization time, can make limiting viscosity is the poly (arylene ether nitrile) sulphone resin of 0.2-1.0dl/g, is suitable for different purposes.
The synthetic novel high-performance polyethers nitrile sulphone resin according to the present invention has excellent heat-resistant stability, and second-order transition temperature Tg=300-350 ℃ is the highest soluble poly aromatic ether nitrile sulphone resin of present heat resisting temperature.This novel poly (arylene ether nitrile) sulphone resin can pass through solution-cast film forming or mold pressing film-making, carries out the test of electrical property, mechanical property etc.The result shows that the limiting viscosity of this resin is the good thermoplastic resin of toughness greater than 0.6dl/g (more preferably greater than 0.8dl/g).Toughness judges with reference to U.S. Pat P4,320,224, make the thick film of 0.2mm with solution casting method, and 180 degree are folding at least 5 times repeatedly, and flawless is to be toughened resin.This resin excellent combination property has characteristics such as very high intensity, excellent electric insulation, radiation resistance, burning self-extinguishing, and can carry out solution-cast film forming, compression molding, extrude, multiple mode such as injection processes.
Below be described in detail most preferred embodiment of the present invention.
Under nitrogen protection, with 142.95g (0.6 mole) 4-(4-hydroxy phenyl) naphthyridine-1-ketone (DHPZ), 51.60g (0.3 mole) 2,6-dichlorobenzonitrile, 86.15g (0.3 mole) 4,4 '-dichloro diphenyl sulfone, 116g (0.84 mole) anhydrous K
2CO
3, 400ml tetramethylene sulfone and 300ml toluene joins in the reactor that agitator, thermometer, reflux water-dividing device and nitrogen inlet are housed, stir, the heat temperature raising reaction, under 160 ℃, azeotropic reflux dewatering 1.5 hours has big water gaging to be steamed separation removal.Then, steam most of toluene.Temperature is raised to 200 ℃, and high temperature polymerization 15-20 hour, reaction system was by the light yellow brown that changes into gradually, and system viscosity obviously increases.After reaction finishes, add tetramethylene sulfone reaction mixture diluted, polymers soln under high-speed stirring, with boiling water as precipitation agent, with the polymkeric substance precipitating, filter, drain.This polymkeric substance 120 ℃ of vacuum-dryings 24 hours, is obtained purified poly (arylene ether nitrile) sulphone resin, and its limiting viscosity is 0.68dl/g, and second-order transition temperature Tg is 315 ℃.
Claims (5)
1. polyaryl ether-nitrile-sulfone that contains phthalazine biphenyl structure is characterized in that constituting and contains following structural unit in this polyaryl ether-nitrile-sulfone molecular chain structure:
R1, R2, R3, R4 can be alkyl, phenyl, hydrogen atom or halogen atom.
2. the preparation method that contains phthalazine biphenyl structure polyethers nitrile sulfone according to claim 1, it is characterized in that, with non-proton type polar solvent or the mixed solvent that contains non-proton type polar solvent is reaction solvent, salt with basic metal or alkaline-earth metal is a catalyzer, with diazanaphthalene terphenyl phenol (DHPZ) monomer and 2,6-two halobenzene nitriles, 4,4 '-dihalo-sulfobenzide monomer is that raw material carries out polyreaction, make the polyaryl ether-nitrile-sulfone that contains phthalazine biphenyl structure through solution nucleophilic substitution step-reaction polymerization, carry out azeotropic dehydration in the reaction process, as azeotropy dehydrant, temperature of reaction is 120～240 ℃, reacts to add precipitation agent after 5～40 hours with alkylbenzene or halogeno-benzene, the polymkeric substance coagulative precipitation is come out, filter, separate, clean, drying obtains polymkeric substance.
3. the preparation method that contains phthalazine biphenyl structure polyethers nitrile sulfone according to claim 1 is characterized in that using the aprotic polar solvent of types such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetramethylene sulfone, n-formyl sarcolysine base pyrrolidone, dimethyl sulfoxide (DMSO) as polymerization solvent; With alcohols, water or the mixing liquid that contains pure water as sinking agent.
4. the preparation method that contains phthalazine biphenyl structure polyethers nitrile sulfone according to claim 1 is characterized in that 4 '-dihalo-benzophenone monomer then contains in the main polymer chain-SO simultaneously if add 4 simultaneously in polymerization system
2-,-the CO-group, then resulting polymers can be described as the polyethers nitrile sulfone ketone that contains phthalazine biphenyl structure.
5. the preparation method that contains phthalazine biphenyl structure polyethers nitrile sulfone according to claim 1 is characterized in that, if added right-(4,4 '-dihalo-dibenzoyl) benzene simultaneously in polymerization system, then contains simultaneously in the main polymer chain-SO
2-,
Then resulting polymers can be described as the polyethers nitrile sulfone ketone ketone that contains phthalazine biphenyl structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03111541 CN1197894C (en) | 2003-04-25 | 2003-04-25 | Polyarylether-nitrile-sulphone contg. diazanaphthaleneone biphenyl structure and preparing process thereof |
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| CN 03111541 CN1197894C (en) | 2003-04-25 | 2003-04-25 | Polyarylether-nitrile-sulphone contg. diazanaphthaleneone biphenyl structure and preparing process thereof |
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| CN1451675A CN1451675A (en) | 2003-10-29 |
| CN1197894C true CN1197894C (en) | 2005-04-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619131B (en) * | 2009-07-25 | 2012-07-25 | 大连理工大学 | O-phthalodinitrile end-blocked soluble polyarylether resin with phthalazinone structure and condensate and preparation method thereof |
| CN104031376B (en) * | 2014-06-17 | 2018-04-17 | 大连理工大学 | Continuous carbon fibre enhancing Phthalazinone poly (arylene ether nitrile) resin based composites and preparation method thereof |
| CN113461943B (en) * | 2021-07-07 | 2022-05-31 | 大连理工大学 | Copolymerized aryl ether sulfone containing bis-phthalazinone structure and preparation method thereof |
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