CN101418072B - Industrial production method of semi-crystalline poly aryl ether nitrile - Google Patents
Industrial production method of semi-crystalline poly aryl ether nitrile Download PDFInfo
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- CN101418072B CN101418072B CN2008103057203A CN200810305720A CN101418072B CN 101418072 B CN101418072 B CN 101418072B CN 2008103057203 A CN2008103057203 A CN 2008103057203A CN 200810305720 A CN200810305720 A CN 200810305720A CN 101418072 B CN101418072 B CN 101418072B
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Abstract
The invention relates to an industrial production method for semi-crystal poly(aromatic ether nitrile), which belongs to the field of polymer material. The method comprises the following steps: 2, 6-dichloro benzonitrile and hydroquinone are taken as raw materials; anhydrous potassium carbonate is taken as a catalyst; in the presence of a solvent and a dehydrating agent, the raw materials and the catalyst react under atmospheric pressure to obtain the poly(aromatic ether nitrile) homopolymer with low molecular weight and regular chain segments; and then the molecular weight of polymer is increased through pressurization, so as to obtain the semi-crystal poly(aromatic ether nitrile) polymer with high molecular weight. Due to the increase of crystallinity and molecular weight, the mechanical properties and heat resistance of the semi-crystal poly(aromatic ether nitrile) polymer are obviously improved.
Description
Technical field
The present invention relates to a kind of industrialized preparing process of semi-crystalline poly aryl ether nitrile, belong to polymeric material field.
Background technology
Poly aryl ether nitrile (Polyarylene ether ether nitriles, PEEN) be the polymkeric substance that a class has special molecular structure, because strong polarity cyano group (introducing CN), strengthen the effect of molecule interchain dipole-dipole, can obtain higher heat resistance and physical strength, insulating property etc.; While occurs as side group owing to cyano group, and is less to the moulding processability influence of polymkeric substance, particularly has at high temperature still can keep stable performance in the environment of use and temperature variation continuously, and the while flame retardant rating can reach outstanding features such as VO level.Militarily be used for the manufacturing of electronic weaponry, electronics big gun, ballistic missile, particle accelerator; In machinofacture, have a wide range of applications in auto parts, the laser system; Aspect aerospace, also be indispensable material in satellite manufacturing and the space technology exploitation.
Nineteen seventies begins, the investigator of state such as the U.S., Japan carried out the synthetic improvement to the polyarylether polymkeric substance, but had only for example du pont company, and a few companies such as Britain ICI can produce the polyarylether polymkeric substance, as PEEK, so price is very expensive.The present inventor has studied a kind of industrialized preparing process (seeing Chinese patent 200610038381.8) of poly aryl ether nitrile, but this method production process remains under high pressure, has adopted two kinds of dihydric phenols simultaneously.What this method obtained is random copolymerization structure poly (arylene ether nitrile), is difficult to crystallization, belongs to amorphous structure, because feed composition causes possible side reaction many more, the molecular weight distribution of generation is wide.There is the lower shortcoming of modulus, intensity and thermotolerance in this amorphous polymer, and its tensile strength can only reach about 90MPa, and modulus is at 1500-2000MPa.Therefore this area needs a kind of method of suitability for industrialized production semi-crystalline poly aryl ether nitrile.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of simple suitability for industrialized production semi-crystalline poly aryl ether nitrile.
Technical scheme of the present invention:
It is with 2,6-dichlorobenzonitrile and Resorcinol are raw material, make catalyzer with Anhydrous potassium carbonate, in the presence of solvent, dewatering agent, 100～160 ℃ of reactions obtain the regular small molecular weight poly aryl ether nitrile homopolymer of segment under normal pressure, by being forced into 2-5Mpa, 180～300 ℃ of reactions improve polymericular weight, thereby obtain high-molecular weight semi-crystalline poly aryl ether nitrile polymkeric substance then.
Further, it is to be finished by following steps:
A, take by weighing raw material according to following weight proportion: 2,6-dichlorobenzonitrile: Resorcinol: Anhydrous potassium carbonate: dewatering agent=110～150: 70～96: 102～148: 16～30;
Preferably: 2,6-dichlorobenzonitrile: Resorcinol: Anhydrous potassium carbonate: dewatering agent=137.6: 88: 132: 20.
B, above-mentioned raw materials drop into autoclave with solvent, after stirring under the condition of normal pressure, reactor are warming up to 100～160 ℃, and insulation refluxed 2～6 hours;
Reaction equation:
C, reactor temperature is risen to 180～300 ℃, pressure rises to 2-5Mpa, and insulation reaction 2～6 hours is put into product in the methanol extraction still, and the throw out that obtains promptly gets semi-crystalline poly aryl ether nitrile through methanol wash, drying, granulation.
n＝1000-1500
Wherein, solvent of the present invention can be: NMP; Described dewatering agent can be a toluene.
Further, the water byproduct that the reaction of b step can be generated is disposed to the waste water storage tank from water trap, help focusing on the realization environment protection emission, the dewatering agent (toluene) on reactor upper strata is told from water trap delivered to the rectifying recovery tower, help recycling and reducing cost.And will react the liquid that generates easily and separate with dewatering agent.
The present invention is with 2, the 6-dichlorobenzonitrile is a raw material, making catalyzer, NMP etc. with Anhydrous potassium carbonate makes solvent, toluene etc. and makes dewatering agent, the hemihedral crystal poly aryl ether nitrile that utilizes Resorcinol to prepare compound with regular structure has the characteristics of accelerated reaction, in earlier stage under normal pressure, obtain the regular small molecular weight poly aryl ether nitrile homopolymer of segment in reaction, improve polymericular weight by compressive reaction then, thereby obtain high-molecular weight semi-crystalline poly aryl ether nitrile polymkeric substance.The poly aryl ether nitrile polymer of the present invention's exploitation is owing to the increase of its degree of crystallinity and molecular weight, and its mechanical property and thermotolerance are improved significantly.Simultaneously, working condition of the present invention is easy to realize that production process is easy to control, the semi-crystalline poly aryl ether nitrile that adopts present method to make, and cost is low, good combination properties such as mechanical property and resistance toheat.
Superiority of the present invention is:
(1) adopted that next step is reinforced in condition of normal pressure, working condition is easy to realize that production process is easy to control, is applicable to suitability for industrialized production.
(2) adopt a kind of dihydric phenol as raw material, reduced multiple dihydric phenol synthetic competition side reaction, obtain the regular small molecular weight poly aryl ether nitrile homopolymer of segment at reaction solution under normal pressure in early stage, improve polymericular weight by compressive reaction then, thereby obtain high-molecular weight semi-crystalline poly aryl ether nitrile polymkeric substance, reduce the molecular weight distribution of semi-crystalline poly aryl ether nitrile polymkeric substance, improved the mechanical property and the resistance toheat of polymkeric substance.
(3) in synthetic, adopt the dual function of direct nucleophilic substitution reaction and toluene dewatering agent to obtain the high-molecular weight semi-crystalline poly aryl ether nitrile, overcome the side reaction in the polymerization process and the generation of by product effectively, guaranteed purity and the performance stable homogeneous of semi-crystalline poly aryl ether nitrile.
(4) be that the Molecular Structure Design that side chain, complete fragrant structure are the semi-crystalline poly aryl ether nitrile of main chain is the basic characteristics of this project with the CN base, both guarantee the thermotolerance and the physicalies such as high strength, high-modulus of product, guaranteed its potential reactable functional performance again.
(5) semi-crystalline poly aryl ether nitrile of Huo Deing is the speciality polymer material of a class from the fire-retardant VO of reaching level, for the environmental protectionization of machinery, automobile, electronics, Aerospace Products provides new functional materials.
Embodiment
The preparation of embodiment 1 semi-crystalline poly aryl ether nitrile of the present invention
(1) get the raw materials ready:
412.8 kilograms of 2,6 dichlorobenzonitriles
264 kilograms of Resorcinol
396 kilograms of Anhydrous potassium carbonates (catalyzer)
748 kilograms of solvent NMP
60 kilograms of toluene
(2) ready reaction still:
Reactor top in sealing connects water trap by valve, connects vapour-discharge tube by valve above reactor.
(3) production process:
1, above-mentioned each raw material is dropped into reactor in order, stir.
2, under condition of normal pressure, reactor is warming up to 160 ℃, is incubated 2 hours, the back flow reaction of dewatering, the water of generation directly is disposed to the waste water storage tank from water trap, and toluene is told from water trap and is delivered to the rectifying recovery tower.Reactor temperature is risen to 220 ℃ again, pressure rises to 2MPa, is incubated 4 hours.
3, discharging: the reactant in the reactor is released in the methanol extraction still.
4, filter, throw out is 220 ℃ a dryer inner drying in temperature after methanol wash two to three times, and granulation then makes purity and be 99.0% semi-crystalline poly aryl ether nitrile.
Product performance detect:
n＝1000-1500
Differential scanning calorimeter (DSC) characterizes: glass transition temperature Tg is 160 ℃, 312.5 ℃ of fusing points.
Mechanical property: tensile strength 119Mpa, flexural strength 149Mpa; Add 40% glass back draft intensity 185.94Mpa, flexural strength 263.45Mpa; Notched Izod impact strength 8.9KJ/m
2
Modulus: greater than 3000MPa.
Resistance toheat: heat-drawn wire surpasses 240 ℃, and working temperature is 50-280 ℃.
Ageing-resistant performance: 200 ℃ of thermal ageings are 72 hours in the air ambient, and its mechanical property is because the increase of degree of crystallinity improves 8% on the contrary.
Chemical resistance: except that the vitriol oil, finding as yet at present can be at the solvent of the semi-crystalline poly aryl ether nitrile of dissolving below 200 ℃, strong to mineral acid, alkali and salt erosion resistance.
The preparation of embodiment 2 semi-crystalline poly aryl ether nitriles of the present invention
(1) get the raw materials ready:
329.6 kilograms of 2,6 dichlorobenzonitriles
211 kilograms of Resorcinol
316.8 kilograms of Anhydrous potassium carbonates (catalyzer)
565 kilograms of solvent NMP
50 kilograms of toluene
(2) ready reaction still:
Reactor top in sealing connects water trap by valve, connects vapour-discharge tube by valve above reactor.
(3) production process:
1, above-mentioned each raw material is dropped into reactor in order, stir.
2, under condition of normal pressure, reactor is warming up to 150 ℃, is incubated 3 hours, the back flow reaction of dewatering, the water of generation directly is disposed to the waste water storage tank from water trap, and toluene is told from water trap and is delivered to the rectifying recovery tower.Reactor temperature is risen to 200 ℃ again, pressure rises to 2MPa, is incubated 2 hours.
3, discharging: the reactant in the reactor is released in the methanol extraction still.
4, filter, throw out is 220 ℃ a dryer inner drying in temperature after methanol wash two to three times, and granulation then makes purity and be 99.0% semi-crystalline poly aryl ether nitrile.
Product performance detect:
Differential scanning calorimeter (DSC) characterizes: glass transition temperature Tg is 158 ℃, 312.25 ℃ of fusing points.
Mechanical property: tensile strength 113Mpa, flexural strength 147Mpa; Add 40% glass back draft intensity 166Mpa, flexural strength 237Mpa; Notched Izod impact strength 8.2KJ/m
2
Modulus: greater than 3000Mpa.
Resistance toheat: heat-drawn wire surpasses 233 ℃, and working temperature is 50-220 ℃.
Ageing-resistant performance: 200 ℃ of thermal ageings are 72 hours in the air ambient, and its mechanical property is because the increase of degree of crystallinity improves 5% on the contrary.
Chemical resistance: except that the vitriol oil, finding as yet at present can be at the solvent of the semi-crystalline poly aryl ether nitrile of dissolving below 200 ℃, strong to mineral acid, alkali and salt erosion resistance.
The preparation of embodiment 3 semi-crystalline poly aryl ether nitriles of the present invention
(1) get the raw materials ready:
329.6 kilograms of 2,6 dichlorobenzonitriles
211 kilograms of Resorcinol
316.8 kilograms of Anhydrous potassium carbonates (catalyzer)
565 kilograms of solvent NMP
50 kilograms of toluene
(2) ready reaction still:
Reactor top in sealing connects water trap by valve, connects vapour-discharge tube by valve above reactor.
(3) production process:
1, above-mentioned each raw material is dropped into reactor in order, stir.
2, under condition of normal pressure, reactor is warming up to 140 ℃, is incubated 5 hours, the back flow reaction of dewatering, the water of generation directly is disposed to the waste water storage tank from water trap, and toluene is told from water trap and is delivered to the rectifying recovery tower.Reactor temperature is risen to 260 ℃ again, pressure rises to 2MPa, is incubated 2 hours.
3, discharging: the reactant in the reactor is released in the methanol extraction still.
4, filter, throw out is 220 ℃ a dryer inner drying in temperature after methanol wash two to three times, and granulation then makes purity and be 99.0% semi-crystalline poly aryl ether nitrile.
Product performance detect:
Differential scanning calorimeter (DSC) characterizes: glass transition temperature Tg is 159 ℃, 313 ℃ of fusing points.
Mechanical property: tensile strength 115Mpa, flexural strength 138Mpa; Add 40% glass back draft intensity 170Mpa, flexural strength 240Mpa; Notched Izod impact strength 8.0KJ/m
2
Modulus: greater than 3000Mpa.
Resistance toheat: heat-drawn wire surpasses 238 ℃, and working temperature is 50-220 ℃.
Ageing-resistant performance: 200 ℃ of thermal ageings are 72 hours in the air ambient, and its mechanical property is because the increase of degree of crystallinity improves 8% on the contrary.
Chemical resistance: except that the vitriol oil, finding as yet at present can be at the solvent of the semi-crystalline poly aryl ether nitrile of dissolving below 200 ℃, strong to mineral acid, alkali and salt erosion resistance.
In a word, the semi-crystalline poly aryl ether nitrile that adopts the inventive method to obtain all obtains bigger raising at mechanical property, heat resistance, chemical-resistance etc., the advantage that has kept simultaneously the poly aryl ether nitrile, in high temperature, high temperature, high humidity, high-frequency environment, has very high specific insulation, surface resistivity, dielectric constant and electrical loss tangent, the while good stability of the dimension, hot swelling coefficient is little, creep is low, and water absorption rate is low, and molding shrinkage is little, even at high temperature also show good dimensional stability, it is a kind of polymer of high comprehensive performance.
Claims (4)
1. the industrialized preparing process of a semi-crystalline poly aryl ether nitrile, it is characterized in that: it is with 2,6-dichlorobenzonitrile and Resorcinol are raw material, make catalyzer with Anhydrous potassium carbonate, in the presence of solvent, dewatering agent, 100～160 ℃ of reactions obtain the regular small molecular weight poly aryl ether nitrile homopolymer of segment under normal pressure, and by being forced into 2-5Mpa, 180～300 ℃ of reactions obtain high-molecular weight semi-crystalline poly aryl ether nitrile polymkeric substance then; Wherein, described dewatering agent is a toluene; Described solvent is: NMP.
2. the industrialized preparing process of semi-crystalline poly aryl ether nitrile according to claim 1 is characterized in that it being to be finished by following steps:
A, take by weighing raw material according to following weight proportion: 2,6-dichlorobenzonitrile: Resorcinol: Anhydrous potassium carbonate: dewatering agent=110～150: 70～96: 102～148: 16～30;
B, above-mentioned raw materials drop into autoclave with solvent, after stirring under the condition of normal pressure, reactor are warming up to 100～160 ℃, and insulation refluxed 2～6 hours;
C, reactor temperature is risen to 180～300 ℃, pressure rises to 2-5Mpa, reacts 2～6 hours, and product is added in the methyl alcohol, and the throw out that obtains promptly gets semi-crystalline poly aryl ether nitrile through methanol wash, drying, granulation.
3. the industrialized preparing process of semi-crystalline poly aryl ether nitrile according to claim 2 is characterized in that:
2,6-dichlorobenzonitrile: Resorcinol: Anhydrous potassium carbonate: dewatering agent=137.6: 88: 132: 20.
4. the industrialized preparing process of semi-crystalline poly aryl ether nitrile according to claim 2, it is characterized in that: the water byproduct of b step directly is disposed to the waste water storage tank from water trap, and dewatering agent is told from water trap and is delivered to the rectifying recovery tower.
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| CN102492131B (en) * | 2011-11-28 | 2014-04-23 | 电子科技大学 | Polyaryl ether nitrile resin, polyaryl ether nitrile film and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567248A (en) * | 1983-12-15 | 1986-01-28 | Basf Aktiengesellschaft | Branched, high molecular weight, thermoplastic polyarylene ethers containing nitrile groups, and their preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4567248A (en) * | 1983-12-15 | 1986-01-28 | Basf Aktiengesellschaft | Branched, high molecular weight, thermoplastic polyarylene ethers containing nitrile groups, and their preparation |
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