CN106674979A - Silane-modified cyan carbon nanotube compound polyarylene ether nitrile composite material and preparation method thereof - Google Patents
Silane-modified cyan carbon nanotube compound polyarylene ether nitrile composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silane-modified cyan carbon nanotube compound polyarylene ether nitrile composite material, which is prepared from the following raw materials in parts by weight: 1.7-2 parts of 4-nitrophthalonitrile, 18-20 parts of multiwalled carbon nanotubes, 0.6-1 part of p-aminophenol, 58-70 parts of thionyl chloride, 100-130 parts of poly arylene ether nitrile, 2-3 parts of potassium zirconium carbonate, 1-2 parts of 2-ethylhexyl acrylate, 0.1-0.2 part of alkylated diphenylamine, 0.6-1 part of zinc dibutyl dithiocarbamate, 3-4 parts of polyethylene adipate glycol, 1-2 parts of borax, 0.7-1.8 parts of hexamethylphosphoramide, 0.4-1 part of 8-hydroxyquinoline, 2-3 parts of cyanoethyl cellulose, 0.08-0.1 part of silane coupling agent kh560 and a proper amount of dimethylformamide, sulfuric acid, nitric acid and acetone. The material is good in tenacity, high in impact strength, long in service life and excellent in overall performance.
Description
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of compound polyarylether of silane-modified cyano group CNT
Nitrile composite and preparation method thereof.
Background technology
Poly (arylene ether nitrile) is the hemicrystalline macromolecule of a class excellent combination property, with mechanical strength very high, anti-flammability,
The advantages of heat resistance and creep resistance, it is expected to played a significant role in fields such as auto industry, electronic apparatus and space flight and aviation.
The subject matter that limitation PEN is applied in special type function material in a very long time is the synthesis cost of polymer P EN
And processing fluidity.This seminar has grasped PEN low cost synthetic technologys by years of researches, have developed a series of
The PEN polymer of different demands is adapted to, while have developed with prepolymer phthalonitrile（BPH）As PEN resins
Plasticizer, significantly improves the processing fluidity of PEN.In addition, the intrinsic property of material such as mechanical strength, electrical property
Energy and heat endurance etc. are also the principal element for influenceing materials application.Therefore in order to widen PEN in space flight and aviation and electronics etc.
The application in field, researcher wishes to make it obtain excellent performance by the modified of PEN, eventually becomes a kind of widely used
High-performance special engineering material.
CNT is a kind of monodimension nanometer material, with the excellent physics such as high intensity, high length-diameter ratio, light weight and change
Learn property.In recent years, going deep into CNT and nano materials research, its wide application prospect also constantly shows
Come.A small amount of CNT is incorporated into polymeric matrix, you can assign the excellent mechanical property of material and barrier property, good
Good hot property and dimensional stability, distinctive anti-flammability and special optical property, thus polymer/carbon nano-tube composite wood
Material receives the extensive concern of investigation of materials person, becomes the focus of current or even investigation of materials in future, but due to Van der Waals
The effect of power, CNT is typically easy to reunite, therefore simple CNT is difficult to realize and divides in polymer composites
Dissipate.When high-performance polymer/carbon nano tube compound material is prepared, in order to realize CNT single dispersing, align with
And the interface interaction power between enhancing CNT and polymer, it is huge challenge to introduce monodispersed CNT.Carbon is received
The functionalization of mitron is a kind of effective way for preventing it from reuniting, while may also help in CNT more preferably, more stably dividing
It is dispersed in the matrix resin of polymer；
The functionalization of CNT is a kind of effective way for preventing it from reuniting, while may also help in CNT more preferably, more
It is dispersed stably in the matrix resin of polymer.The document reported shows, by CNT at ultrasonic disperse in nitration mixture
Reason 2h, is capable of achieving carbon nano tube surface carboxylated.And pass through amidation process, can further realize the work(of CNT
Energyization.The enhancing of interface adhesion can be realized by polarization with other functional groups due to the cyano group on poly (arylene ether nitrile) aromatic ring,
Therefore the present invention selects to use 4- amino phenoxy phthalonitrile grafting carbon nanotubes, so as to realize the cyanalation of CNT.
Cyanalation CNT can be not only dispersed stably in the intensive polar solvents such as DMF and NMP, can also be in certain bar
There is cyano group cross-linking reaction with poly (arylene ether nitrile) under part.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of silane-modified cyano group CNT is combined
Poly (arylene ether nitrile) composite material and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of silane-modified cyano group CNT is combined poly (arylene ether nitrile) composite material, and it is made up of the raw material of following weight parts
's：
4- nitrophthalonitriles 1.7-2, multi-walled carbon nano-tubes 18-20, p-aminophenol 0.6-1, thionyl chloride 58-70, poly- virtue
Ether nitrile 100-130, potassium zirconium carbonate 2-3, Isooctyl acrylate monomer 1-2, alkylated diphenylamine 0.1-0.2, dibutyl dithio amino
Zinc formate 0.6-1, polyadipate ethylene glycol 3-4, borax 1-2, HMPA 0.7-1,8-hydroxyquinoline 0.4-1, cyanogen
Ethyl cellulose 2-3, silane coupler kh5600.08-0.1, dimethylformamide, sulfuric acid, nitric acid, acetone in proper.
A kind of preparation method of the compound poly (arylene ether nitrile) composite material of described silane-modified cyano group CNT, including it is following
Step：
（1）Above-mentioned 4- nitrophthalonitriles, p-aminophenol are mixed, the dimethyl methyl of 27-30 times of compound weight is added to
In acid amides, stirring reaction 6-7 hours at 80-90 DEG C, be placed in precipitation in 80-90 DEG C of baking oven and be vacuum dried 20-25 by filtering
Hour, obtain cyaniding auxiliary agent；
（2）Above-mentioned potassium zirconium carbonate is added in the deionized water of 36-40 times of its weight, is stirred, liter high-temperature is 60-70
DEG C, above-mentioned cyanethyl cellulose is added, insulated and stirred 10-14 minutes, the hydrochloric acid of 1-2mol/l is added dropwise, regulation pH is 1-2, stirring
Reaction 20-30 minutes, mixes with above-mentioned multi-walled carbon nano-tubes, ultrasonic 3-5 minutes, filtering, by precipitation washing 2-3 times, in 47-50
It is vacuum dried 1-2 hours at DEG C, obtains modified multiwalled carbon nanotube；
（3）Above-mentioned modified multiwalled carbon nanotube is taken, volume ratio is added to for 3-4:It is described in 1 sulfuric acid, the mixed solution of nitric acid
Sulfuric acid concentration for 95-97%, nitric acid concentration be 91-95%, ultrasound 20-25 hours, suction filtration, will be deposited at 60-65 DEG C
It is vacuum dried 1-2 hours at 100-105 DEG C, discharging cooling is added in above-mentioned thionyl chloride, it is 70-75 DEG C to rise high-temperature, plus
Enter the dimethylformamide of mixed system weight 1-2%, insulated and stirred 20-22 hours, suction filtration, by precipitation toluene, dimethyl methyl
Acid amides is washed 2-3 times successively, air drying, obtains acyl chlorides carbon nano tube；
（4）Above-mentioned 8-hydroxyquinoline, borax are mixed, is added in the acetone of 25-30 times of compound weight, stirred, plus
Enter above-mentioned polyadipate ethylene glycol, it is 80-90 DEG C to rise high-temperature, adds above-mentioned acyl chlorides carbon nano tube, dibutyl dithio ammonia
Base zinc formate, insulated and stirred 1-2 hours, obtains acetone dispersion liquor；
（5）The different monooctyl ester of aforesaid propylene acid, cyaniding auxiliary agent are mixed, is added in the acetone of 40-50 times of compound weight, stirring is equal
It is even, above-mentioned acetone dispersion liquor is added, precipitation acetone, deionized water are washed 2-3 times in ultrasonic 15-20 hours, filtering successively,
Dried at 80-90 DEG C of vacuum 1-2 hours, obtain cyano group CNT；
（6）Above-mentioned poly (arylene ether nitrile) is added in the dimethylformamide of 16-20 times of its weight, is stirred, obtain acid amides dispersion
Liquid；
（7）Above-mentioned cyano group CNT is added in the dimethylformamide of 100-110 times of its weight, it is ultrasonic 20-30 minutes,
It is sent in 190-200 DEG C of oil bath, insulated and stirred 25-30 minutes, discharges, above-mentioned acid amides dispersion liquid, stirring reaction 80- is added dropwise
100 minutes, remaining each raw material is added, stirred, suction filtration is vacuum dried 30-40 minutes at being deposited in 60-70 DEG C, cooling,
Obtain final product.
It is an advantage of the invention that：For pure multi-walled carbon nano-tubes, its surface is for nonpolar, and pure multi-walled carbon nano-tubes
There is strong Van der Waals force between pipe, so the bad dispersibility in poly (arylene ether nitrile) resin matrix, easily reunites, the carbon nanometer of reunion
Pipe can not only be reduced and the interfacial contact area between polyarylether matrix, reduce the transmission efficiency of extraneous load, and can the group of causing
Poly- CNT turns into stress concentration point, and for the pure multi-walled carbon nano-tubes of cyano group functionalization, it is addition agent modified through cyaniding
Its surface is in polarity afterwards, and the compatibility with poly (arylene ether nitrile) resin is preferable, thus the pure multi-walled carbon nano-tubes of cyano group functionalization is in poly- virtue
There is dispersiveness more more preferable than pure multi-walled carbon nano-tubes, good dispersiveness causes that cyano group functionalization is pure more in ether nitrile resin matrix
There is bigger contact interface between wall carbon nano tube and poly (arylene ether nitrile) resin matrix, form with 4- amino-benzene oxygens neighbour's benzene two
Formonitrile HCN is flexible layer, and rigid multi-walled carbon nano-tubes is the core/shell structure of core, because cyaniding auxiliary agent end has-CN functional groups,
There is polarity effect between its-CN group with poly (arylene ether nitrile), so as to improve cyano group functionalized carbon nano-tube and poly (arylene ether nitrile) tree
, due to huge specific surface area, there is very big interface between Nano filling and resin matrix in the interfacial bond property between aliphatic radical body
Contact, when composite by external force when being acted on, this interracial contact provides effective approach for stress transmission, therefore,
Cyano group CNT is added in poly (arylene ether nitrile) resin, because it has effective phase interaction between poly (arylene ether nitrile) resin matrix
With, the final intensity of composite and modulus with pure poly (arylene ether nitrile) resin matrix phase than there is larger enhancing；Therefore improve
The mechanical property of composite；
Toughness of material of the invention is good, excellent in cushion effect, and long service life, combination property is superior.
Specific embodiment
A kind of silane-modified cyano group CNT is combined poly (arylene ether nitrile) composite material, and it is by the raw material system of following weight parts
Into：
4 nitrophthalonitriles 1.7, multi-walled carbon nano-tubes 18, p-aminophenol 0.6, thionyl chloride 58, poly (arylene ether nitrile) 100, carbonic acid
Zirconium potassium 2, Isooctyl acrylate monomer 1, alkylated diphenylamine 0.1, zinc dibutyl dithiocarbamate 0.6, polyadipate ethylene glycol
3rd, borax 1, HMPA 0.7,8 oxyquinolines 0.4, cyanethyl cellulose 2, silane coupler kh5600.08, diformazan
Base formamide, sulfuric acid, nitric acid, acetone in proper.
A kind of preparation method of the compound poly (arylene ether nitrile) composite material of described silane-modified cyano group CNT, including it is following
Step：
（1）Above-mentioned 4 nitrophthalonitrile, p-aminophenol are mixed, the dimethylformamide of 27 times of compound weight is added to
In, be placed in precipitation in 80 DEG C of baking oven and be vacuum dried 20 hours by stirring reaction 6 hours at 80 DEG C, filtering, obtains cyaniding and helps
Agent；
（2）Above-mentioned potassium zirconium carbonate is added in the deionized water of 36 times of its weight, is stirred, it is 60 DEG C to rise high-temperature, plus
Enter above-mentioned cyanethyl cellulose, insulated and stirred 10 minutes is added dropwise the hydrochloric acid of 1mol/l, and regulation pH is 1, stirring reaction 20 minutes,
Mix with above-mentioned multi-walled carbon nano-tubes, ultrasound 3 minutes, filtering, precipitation washing 2 times is vacuum dried 1 hour at 47 DEG C, obtain
Modified multiwalled carbon nanotube；
（3）Above-mentioned modified multiwalled carbon nanotube is taken, it is 3 to be added to volume ratio:It is described in 1 sulfuric acid, the mixed solution of nitric acid
Sulfuric acid concentration is that the concentration of 95%, nitric acid is 91%, and ultrasound 20 hours at 60 DEG C, suction filtration is vacuum dried at being deposited in 100 DEG C
1 hour, discharging cooling was added in above-mentioned thionyl chloride, and it is 70 DEG C to rise high-temperature, adds the dimethyl of mixed system weight 1%
Formamide, insulated and stirred 20 hours, suction filtration washs precipitation toluene, dimethylformamide 2 times successively, and air drying obtains acyl
Chlorination CNT；
（4）Above-mentioned 8 oxyquinoline, borax are mixed, is added in the acetone of 25 times of compound weight, stirred, in addition
Polyadipate ethylene glycol is stated, it is 80 DEG C to rise high-temperature, adds above-mentioned acyl chlorides carbon nano tube, dibutyl dithiocaarbamate
Zinc, insulated and stirred 1 hour, obtains acetone dispersion liquor；
（5）The different monooctyl ester of aforesaid propylene acid, cyaniding auxiliary agent are mixed, are added in the acetone of 40 times of compound weight, stirred,
Above-mentioned acetone dispersion liquor is added, ultrasound 15 hours, filtering is washed precipitation acetone, deionized water 2 times, 80 DEG C of vacuum successively
Lower drying 1 hour, obtains cyano group CNT；
（6）Above-mentioned poly (arylene ether nitrile) is added in the dimethylformamide of 16 times of its weight, is stirred, obtain acid amides dispersion liquid；
（7）Above-mentioned cyano group CNT is added in the dimethylformamide of 100 times of its weight, ultrasound 20 minutes is sent to
In 190 DEG C of oil bath, insulated and stirred 25 minutes, discharging is added dropwise above-mentioned acid amides dispersion liquid, and stirring reaction 80 minutes is added remaining
Each raw material, is stirred, suction filtration, is vacuum dried 30 minutes at being deposited in 60 DEG C, and cooling is obtained final product.
Performance test:
Tensile strength（MPa）:189.5；
Notch impact strength（KJ/m2）：8.5.
Claims (2)
1. a kind of silane-modified cyano group CNT is combined poly (arylene ether nitrile) composite material, it is characterised in that it is by following weight
What the raw material of part was made：
4- nitrophthalonitriles 1.7-2, multi-walled carbon nano-tubes 18-20, p-aminophenol 0.6-1, thionyl chloride 58-70, poly- virtue
Ether nitrile 100-130, potassium zirconium carbonate 2-3, Isooctyl acrylate monomer 1-2, alkylated diphenylamine 0.1-0.2, dibutyl dithio amino
Zinc formate 0.6-1, polyadipate ethylene glycol 3-4, borax 1-2, HMPA 0.7-1,8-hydroxyquinoline 0.4-1, cyanogen
Ethyl cellulose 2-3, silane coupler kh5600.08-0.1, dimethylformamide, sulfuric acid, nitric acid, acetone in proper.
2. a kind of silane-modified cyano group CNT as claimed in claim 1 is combined the preparation side of poly (arylene ether nitrile) composite material
Method, it is characterised in that comprise the following steps：
（1）Above-mentioned 4- nitrophthalonitriles, p-aminophenol are mixed, the dimethyl methyl of 27-30 times of compound weight is added to
In acid amides, stirring reaction 6-7 hours at 80-90 DEG C, be placed in precipitation in 80-90 DEG C of baking oven and be vacuum dried 20-25 by filtering
Hour, obtain cyaniding auxiliary agent；
（2）Above-mentioned potassium zirconium carbonate is added in the deionized water of 36-40 times of its weight, is stirred, liter high-temperature is 60-70
DEG C, above-mentioned cyanethyl cellulose is added, insulated and stirred 10-14 minutes, the hydrochloric acid of 1-2mol/l is added dropwise, regulation pH is 1-2, stirring
Reaction 20-30 minutes, mixes with above-mentioned multi-walled carbon nano-tubes, ultrasonic 3-5 minutes, filtering, by precipitation washing 2-3 times, in 47-50
It is vacuum dried 1-2 hours at DEG C, obtains modified multiwalled carbon nanotube；
（3）Above-mentioned modified multiwalled carbon nanotube is taken, volume ratio is added to for 3-4:It is described in 1 sulfuric acid, the mixed solution of nitric acid
Sulfuric acid concentration for 95-97%, nitric acid concentration be 91-95%, ultrasound 20-25 hours, suction filtration, will be deposited at 60-65 DEG C
It is vacuum dried 1-2 hours at 100-105 DEG C, discharging cooling is added in above-mentioned thionyl chloride, it is 70-75 DEG C to rise high-temperature, plus
Enter the dimethylformamide of mixed system weight 1-2%, insulated and stirred 20-22 hours, suction filtration, by precipitation toluene, dimethyl methyl
Acid amides is washed 2-3 times successively, air drying, obtains acyl chlorides carbon nano tube；
（4）Above-mentioned 8-hydroxyquinoline, borax are mixed, is added in the acetone of 25-30 times of compound weight, stirred, plus
Enter above-mentioned polyadipate ethylene glycol, it is 80-90 DEG C to rise high-temperature, adds above-mentioned acyl chlorides carbon nano tube, dibutyl dithio ammonia
Base zinc formate, insulated and stirred 1-2 hours, obtains acetone dispersion liquor；
（5）The different monooctyl ester of aforesaid propylene acid, cyaniding auxiliary agent are mixed, is added in the acetone of 40-50 times of compound weight, stirring is equal
It is even, above-mentioned acetone dispersion liquor is added, precipitation acetone, deionized water are washed 2-3 times in ultrasonic 15-20 hours, filtering successively,
Dried at 80-90 DEG C of vacuum 1-2 hours, obtain cyano group CNT；
（6）Above-mentioned poly (arylene ether nitrile) is added in the dimethylformamide of 16-20 times of its weight, is stirred, obtain acid amides dispersion
Liquid；
（7）Above-mentioned cyano group CNT is added in the dimethylformamide of 100-110 times of its weight, it is ultrasonic 20-30 minutes,
It is sent in 190-200 DEG C of oil bath, insulated and stirred 25-30 minutes, discharges, above-mentioned acid amides dispersion liquid, stirring reaction 80- is added dropwise
100 minutes, remaining each raw material is added, stirred, suction filtration is vacuum dried 30-40 minutes at being deposited in 60-70 DEG C, cooling,
Obtain final product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122217A (en) * | 2021-04-23 | 2021-07-16 | 西南石油大学 | Carbon-based amphiphilic nano-flow for oil displacement and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122217A (en) * | 2021-04-23 | 2021-07-16 | 西南石油大学 | Carbon-based amphiphilic nano-flow for oil displacement and preparation method thereof |
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