CN106905525B - One kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method - Google Patents
One kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method Download PDFInfo
- Publication number
- CN106905525B CN106905525B CN201710181054.6A CN201710181054A CN106905525B CN 106905525 B CN106905525 B CN 106905525B CN 201710181054 A CN201710181054 A CN 201710181054A CN 106905525 B CN106905525 B CN 106905525B
- Authority
- CN
- China
- Prior art keywords
- aryl
- ether
- perfluorocyclobutanearyl
- itrile group
- ether ketone
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4031—(I) or (II) containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/427—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses one kind to contain itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone), wherein m indicates the degree of polymerization, 10≤X+Y≤50.The synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) that the invention also discloses a kind of, it include: this by perfluorocyclobutanearyl aryl-ether phenol polymer, phenyl-dihalide formonitrile HCN or dihalo para-Phthalonitrile, 4,4 '-difluoro benzophenones and catalyst are placed in solvent, under the effect of N2 stream, after carrying out multiple temperature control reaction, by precipitating, being filtered, washed and being centrifuged drying, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) sample.Prepared has containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) compared with corrosion-and high-temp-resistant energy, radiation hardness, flame retardant property, and has more crosslinking points.
Description
Technical field
The present invention relates to one kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method, belongs to
Polymeric material field.
Background technique
As the range that power cable is applied is more and more wider, different use environments have a different requirements, e.g., high temperature resistant, resistance to low
Temperature, oil resistant, tear-proof, fire-retardant etc..Especially in the case where use condition is special, application environment is complicated, the need of special cable
Ask day it is aobvious protrude, to reliability, the durability of cable, more stringent requirements are proposed.China express railway and urban track traffic dress
Standby to quickly grow, requirement of the manufacturing enterprise to high-speed rail and urban rail dress cable in stock is towards ultra-thin-wall, high-temperature resistant, high oil resistant, high resistant
Combustion direction is developed.The insulating wall thickness of common thin-walled cable is in 0.3mm or more, and institute is equipped in high-speed railway and urban track traffic
The ultra-thin-wall insulated cable insulation wall thickness needed requires to be 0.18mm.Currently, the primary insulation material of cable industry production thin-walled cable
Material is cross-linked polyolefin, due in the CABLE MATERIALS contain more fire retardant, insulation resistance is smaller, cable be easy it is breakdown, and
And the physical mechanical property of cable, there are many deficiencies, insulation wall can not achieve ultra-thin, it is difficult to meet the needs of manufacturing enterprise.Cause
This, production high-temperature resistant, high oil resistant, high fire-retardance a key technology of ultra-thin-wall insulated cable be exactly to study suitable cable
Material.
Poly(aryl ether ketone) is a kind of aromatics thermoplastic special engineering plastic, has good physics and chemical property, thus often
By as CABLE MATERIALS.For example, CN103275458A provides a kind of Polyether-ether-ketocable cable material, by polyether-ether-ketone, polyester ether, gather
The mixing of phenylate, carbimide etc. improves the performance of CABLE MATERIALS, higher, high abrasion, high oil resistant, electrical insulating property with intensity
It is good, and there are the characteristics such as low cigarette, Halogen, fire-retardant, it is suitble to electricity thin-walled cable to squeeze out.CN105542390A provides a kind of resistance to thermal resistance
Cable insulation material is fired, polyether-ether-ketone, chlorinated paraffin, alkyd resin, Lauxite, blanc fixe, asbestos, five bromoethyls are passed through
Benzene, mica powder, low density polyethylene (LDPE), calcinated argil, palm oil, glycerol, aminopropyl trimethoxysilane, bis-phenol, hypo-aluminum orthophosphate,
The mixing of polytetrafluoroethylene (PTFE), modified filler etc..Fire retardant in the cable material formula of the invention is by borate family fire retardant and phosphorus
Nitrogen combustion inhibitor compounds, and adding a small amount of retardant synergist just makes CABLE MATERIALS have good flame retardant effect and excellent suppression cigarette
Effect, the smoke density of the CABLE MATERIALS is low, poison exponent is low.For another example, it is multiple to provide a kind of special cable use by patent CN105400131A
Condensation material, the special cable are made of with composite material following component: polyether-ether-ketone, polyethylene, polyimides mix in proportion
As basis material, molybdenum trioxide polymer-modified using ethene-vinyl acetate copolymer, magnesia are after coupling agent treatment
As flame-retardant additive, passed through as crosslinking catalyst using silicon nitride crystal whisker as reinforcing agent using cumyl peroxide
Melt blending forms composite material and can be realized bad working environments with preferable high temperature resistant property and improved flame retardant effect
Under stability do not reduce.However, formation homogeneous blend is more difficult between above-mentioned polymer, preparation process is required more multiple
It is miscellaneous, and the auxiliary agent of its addition is more, undoubtedly increases product cost, reduces the reliability of cable.As it can be seen that existing to overcome
Many defects in technology need the novel cable material of a kind of high temperature resistant, the high reliablity that fire-retardant, shielding system can be good.
Make wire and cable made of insulation and sheath material with fluoroplastics (such as polytetrafluoroethylene (PTFE), perfluoroethylene-propylene etc.),
The oxygen index (OI) of fluoroplastics material is PE plastics more than 3 times, is 1.5 times of PVC plastic；Its combustion heat release amount is only four points of timber
One of, it is 1/7th of PE plastics；The cigarette generated under similarity condition is more much smaller than PVC material；Its combustion product is to equipment, instrument
The corrosivity ratio PE of device, PVC material are low.In addition to this, the letter of its dielectric constant, dielectric dissipation factor, High Speed Transfer frequency band
The wire and cable of number attenuation ratio other materials is all small, and physical mechanical property is better than other materials.
Poly (arylene ether nitrile) is a kind of high performance engineering plastics containing cyano side group, has excellent high temperature resistant, corrosion-resistant, resistance to
Radiation, fire-retardant, balanced physical mechanical property and fabulous dimensional stability.Due to the introducing of highly polar cyano side group (- CN),
On the one hand the dipole-dipole effect for increasing molecule interchain is conducive to obtaining the same of higher heat resistance and mechanical strength
When, the adhesive force of reinforced resin matrix；On the other hand, cyano can be formed as a potential crosslinking points has more high heat resistance
The network structure of performance.
It is prepared in conclusion cyano and perfluorocyclobutanearyl aryl-ether structure are introduced into poly(aryl ether ketone) main chain by the applicant
Cyano-containing and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) so that the resinoid simultaneously have poly (arylene ether nitrile), polyether-ether-ketone and
The advantages of fluoroplastics.
Summary of the invention
In order to solve the above problem present in the prior art, the present invention provides one kind to contain itrile group and perfluorocyclobutanearyl
Aryl ether structures poly(aryl ether ketone) and its synthetic method, the perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) of this method preparation have good
Good thermal stability and chemical stability.
Technical scheme is as follows:
It is as follows containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone), structural formula that the present invention relates to one kind:
M indicates the degree of polymerization, is positive integer；10≤X+Y≤50.
Wherein, 1≤m≤200.
In addition, the invention also discloses a kind of synthesis side containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone)
Method includes the following steps: perfluorocyclobutanearyl aryl-ether phenol polymer, phenyl-dihalide formonitrile HCN or dihalo para-Phthalonitrile, 4,
4 '-difluoro benzophenones and catalyst are 1:(1~0.1 in molar ratio): (0.1~1): (2~3) are placed in organic solvent and toluene
In the mixed solvent, in N2Under stream effect, after carrying out temperature control reaction twice, reaction solution is poured into deionized water under stiring immediately
Middle precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 2~5h replacement water, it filters afterwards for 24 hours, it will
Sediment is placed in 80 DEG C of vacuum drying ovens dry 10h, obtains containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) sample
Product；The organic solvent uses n,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone.
Wherein, the temperature control twice reaction is prior to 130~150 DEG C 1~5h of reaction, react 3 then at 150~170 DEG C~
10h。
Wherein, the phenyl-dihalide formonitrile HCN uses 2,5- dichlorobenzonitrile or 2,5- difluorobenzonitrile；The dihalo
Para-Phthalonitrile is 2,5- dichloro para-Phthalonitrile or 2,5- dibromo para-Phthalonitrile.
Wherein, wherein the catalyst uses Anhydrous potassium carbonate or natrium carbonicum calcinatum.
Wherein, perfluorocyclobutanearyl aryl-ether phenol polymer synthesis includes the following steps: to dissolve Trifluorovinyl Aryl Ethers
It in diphenyl ether, is placed in 160 DEG C of oil baths after polyase 13 h, obtaining product is perfluorocyclobutanearyl aryl-ether polymer, and trifluoro is added
Vinyl p-methoxyphenyl ether is as end-capping reagent, and the reaction was continued 7h terminates reaction, obtains the perfluor ring for containing methoxyl group in end
Butyl aryl ether polymer, by with BBr3It is polymerizeing containing perfluorocyclobutanearyl aryl-ether phenol for hydroxyl that reaction demethylation, which obtains end,
Object.
Wherein, a mole molar ratio for the perfluorocyclobutanearyl aryl-ether and trifluoro vinyl p-methoxyphenyl ether is
2∶1。
The invention has the following beneficial effects:
1, the present invention synthesizes a kind of containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) for the first time, develops one kind
Novel cable material.
2, one kind that the present invention synthesizes contains itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone), while having poly- virtue
The advantages of ether nitrile, polyether-ether-ketone and fluoroplastics.
3, the present invention is a kind of contains itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone), which has compared with high temperature resistant
Corrosion resistance, radiation hardness, flame retardant property have more crosslinking points.
4, the present invention is a kind of contains itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone), which is situated between
Matter loss factor, High Speed Transfer frequency band signal attenuation ratio commercially available material wire and cable it is small, physical mechanical property also obviously mentions
It is high.
5, a kind of synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) of the present invention, the synthesis side
Method is simple, and synthetic yield is higher, and production cost is low.
Detailed description of the invention
It is infrared containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) that Fig. 1 is that the embodiment of the present invention 2 is obtained
Spectrogram；
Fig. 2 is the IH- containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) that the embodiment of the present invention 2 obtains
NMR spectra.
Specific embodiment
It is several embodiments of the present invention below, further illustrates the present invention, but the present invention is not limited only to this.
The synthesis of perfluorocyclobutanearyl aryl-ether phenol polymer: Trifluorovinyl Aryl Ethers are dissolved in diphenyl ether, are placed in
In 160 DEG C of oil baths after polyase 13 h, obtaining product is perfluorocyclobutanearyl aryl-ether polymer, and trifluoro vinyl is added to methoxybenzene
Base ether envelope is as end agent (molar ratio of monomer and end-capping reagent be 2:1), and the reaction was continued 7h is terminated and reacted, obtains end and contain
Have the perfluorocyclobutanearyl aryl-ether polymer of methoxyl group, by with BBr3Reaction demethylation obtains end and contains perfluor ring for hydroxyl
Butyl aryl ether phenol polymer, passes through gpc analysis: Mn=2450, PDI=1.25.Its synthetic route:
Embodiment 1
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone): it is sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ether phenol polymer, 0.69g (4mmol) 2,5- dichlorobenzonitrile, 3.49g
(16mmol) 4,4 '-difluoro benzophenone, toluene 80mL, DMAc100mL, 5.53g (40mmol) potassium carbonate, in the N of 1mL/s2Stream
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 20 hours, immediately pour into reaction solution in deionized water under stiring
Precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it is filtered after 24 hours,
Drying 10 hours in 80 DEG C of vacuum drying ovens are put the precipitate in, are obtained containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis: Mn=53339, PDI=2.85, yield 96%.Its synthetic route:
Embodiment 2
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone): it is sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ether phenol polymer, 1.03g (6mmol) 2,5- dichlorobenzonitrile, 3.05g
(14mmol) 4,4 '-difluoro benzophenone, toluene 80mL, DMAc100mL, 5.53g (40mmol) potassium carbonate, in the N of 1mL/s2Stream
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 20 hours, immediately pour into reaction solution in deionized water under stiring
Precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it is filtered after 24 hours,
Drying 10 hours in 80 DEG C of vacuum drying ovens are put the precipitate in, are obtained containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis: Mn=54436, PDI=2.95, yield 97.5%, and shows this reality by DSC result of study
The glass transition temperature for applying the poly(aryl ether ketone) sample of example preparation is 175 DEG C, shows synthesized sample by thermal gravimetric analysis results
Originating weightless temperature is 450 DEG C, and the temperature of weightlessness 5% is 467 DEG C.In addition, viscosity test also is carried out to prepared sample, it will
It is dissolved in DMF containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) sample at 25 DEG C, measures its viscosity, as a result table
Bright 0.26dL/g.
Embodiment 3
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone): it is sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ether phenol polymer, 1.37g (8mmol) 2,5- dichlorobenzonitrile, 2.61g
(12mmol) 4,4 '-difluoro benzophenone, toluene 80mL, DMAc100mL, 5.53g (40mmol) potassium carbonate, in the N of 1mL/s2Stream
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 20 hours, immediately pour into reaction solution in deionized water under stiring
Precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it is filtered after 24 hours,
Drying 10 hours in 80 DEG C of vacuum drying ovens are put the precipitate in, are obtained containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis: Mn=52478, PDI=2.75, yield 96.5%.
Embodiment 4
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone): it is sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ether phenol polymer, 1.72g (10mmol) 2,5- dichlorobenzonitrile, 2.18g
(10mmol) 4,4 '-difluoro benzophenone, toluene 80mL, DMAc100mL, 5.53g (40mmol) potassium carbonate, in the N of 1mL/s2Stream
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 20 hours, immediately pour into reaction solution in deionized water under stiring
Precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it is filtered after 24 hours,
Drying 10 hours in 80 DEG C of vacuum drying ovens are put the precipitate in, are obtained containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis: Mn=51432, PDI=2.82, yield 95.3%.
Embodiment 5
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone): it is sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ether phenol polymer, 0.83g (6mmol) 2,5- difluorobenzonitrile, 3.05g
(14mmol) 4,4 '-difluoro benzophenone, toluene 80mL, DMAc100mL, 5.53g (40mmol) potassium carbonate, in the N of 1mL/s2Stream
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 20 hours, immediately pour into reaction solution in deionized water under stiring
Precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it is filtered after 24 hours,
Drying 10 hours in 80 DEG C of vacuum drying ovens are put the precipitate in, are obtained containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis: Mn=54345, PDI=2.85, yield 97%.Its synthetic route:
Embodiment 6
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone): it is sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ether phenol polymer, 1.18g (6mmol) 2,5- dichloro para-Phthalonitrile, 3.05g
(14mmol) 4,4 '-difluoro benzophenone, toluene 80mL, DMAc100mL, 5.53g (40mmol) potassium carbonate, in the N of 1mL/s2Stream
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 20 hours, immediately pour into reaction solution in deionized water under stiring
Precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it is filtered after 24 hours,
Drying 10 hours in 80 DEG C of vacuum drying ovens are put the precipitate in, are obtained containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis: Mn=55647, PDI=2.79, yield 97.5%.Its synthetic route:
Embodiment 7
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone): it is sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ether phenol polymer, 0.98g (6mmol) 2,5- difluoro para-Phthalonitrile, 3.05g
(14mmol) 4,4 '-difluoro benzophenone, toluene 80mL, DMAc100mL, 5.53g (40mmol) potassium carbonate, in the N of 1mL/s2Stream
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 20 hours, immediately pour into reaction solution in deionized water under stiring
Precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it is filtered after 24 hours,
Drying 10 hours in 80 DEG C of vacuum drying ovens are put the precipitate in, are obtained containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis: Mn=54943, PDI=2.78, yield 97.8%.Its synthetic route:
Fig. 1 is the infrared spectrogram containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) of embodiment 2.From figure
In it can be seen that spectrogram in 3056cm-1、1649cm-1、1592cm-1、1496cm-1It is C=C double bond characteristic absorption peak on phenyl ring,
1234cm-1There is Ar-O-Ar specific peak absorbance peak, 2217cm-1The characteristic absorption peak of appearance-CN illustrates difluoro cyano benzene, two
Fluorine benzophenone reacts with hexafluoro bisphenol-a, tentatively infers that product is containing itrile group and perfluorocyclobutanearyl aryl-ether structure accordingly
Poly(aryl ether ketone).
Fig. 2 is the IH- containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) that the embodiment of the present invention 2 obtains
NMR spectra.7.85,7.83,7.79,7.78,7.76,7.73 and δ of δ 7.42,7.14,7.23,7.22 is cyano benzene monomer and ketone
Proton peak on phenyl ring in monomer, δ 7.12,7.10,7.08,7.01,6.99,6.95 and 6.93 are proton on phenyl ring in phenol monomer
Peak.
And Mn=53345, point of synthetic are become from perfluorocyclobutanearyl aryl-ether phenol Mn=2450 by gpc analysis
Son amount increases.Polycondensation reaction has occurred in provable perfluorocyclobutanearyl aryl-ether phenol, difluoro cyano benzene and difluoro benzophenone, success
Itrile group and perfluorocyclobutanearyl aryl-ether are introduced into poly(aryl ether ketone) main chain, synthesized linear containing itrile group and perfluorocyclobutanearyl
The poly(aryl ether ketone) of aryl ether structures.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (8)
1. one kind contains itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone), which is characterized in that structural formula is as follows:
M indicates the degree of polymerization, is positive integer；10≤X+Y≤50.
2. one kind as described in claim 1 contains itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone), it is characterised in that:
1≤m≤200。
3. a kind of synthesis side as described in claim 1-2 is any containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone)
Method, which comprises the steps of: by perfluorocyclobutanearyl aryl-ether phenol polymer, phenyl-dihalide formonitrile HCN or dihalo pair
Benzene dicarbonitrile, 4,4 '-difluoro benzophenones and catalyst are 1:(1~0.1 in molar ratio): (0.1~1): (2~3) are placed in organic
In the mixed solution of solvent and toluene, in N2Under stream effect, after carrying out 2 temperature control reactions, reaction solution is fallen under stiring immediately
Entering in deionized water and precipitate, filters, the sediment being obtained by filtration is impregnated with deionized water, and it is primary every 2~5h replacement water, for 24 hours
After filter, the sediment after immersion treatment is placed in 80 DEG C of vacuum drying ovens dry 10h, is obtained containing itrile group and perfluorocyclobutanearyl
Aryl ether structures poly(aryl ether ketone) sample；The organic solvent uses n,N-dimethylacetamide, dimethyl sulfoxide or N- methylpyrrole
Alkanone.
4. a kind of synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) as claimed in claim 3,
It is characterized by: 2 temperature controls reaction is prior to 130~150 DEG C 1~5h of reaction, then at 150~170 DEG C of 3~10h of reaction.
5. a kind of synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) as claimed in claim 3,
It is characterized by: the phenyl-dihalide formonitrile HCN uses 2,5- dichlorobenzonitrile or 2,5- difluorobenzonitrile；The dihalo pair
Benzene dicarbonitrile uses 2,5- dichloro para-Phthalonitrile or 2,5- dibromo para-Phthalonitrile.
6. a kind of synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) as claimed in claim 3,
It is characterized by: the catalyst uses Anhydrous potassium carbonate or natrium carbonicum calcinatum.
7. a kind of synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) as claimed in claim 3,
It is characterized by: the synthesis of perfluorocyclobutanearyl aryl-ether phenol polymer includes the following steps: for Trifluorovinyl Aryl Ethers to be dissolved in
It in diphenyl ether, is placed in 160 DEG C of oil baths after polyase 13 h, obtaining product is perfluorocyclobutanearyl aryl-ether polymer, and trifluoro second is added
Alkenyl p-methoxyphenyl ether is as end-capping reagent, and the reaction was continued 7h terminates reaction, obtains the perfluor ring fourth for containing methoxyl group in both ends
Base aryl ether polymer, by with BBr3It is polymerizeing containing perfluorocyclobutanearyl aryl-ether phenol for hydroxyl that reaction demethylation, which obtains end,
Object.
8. a kind of synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) as claimed in claim 7,
It is characterized by: mole molar ratio of the perfluorocyclobutanearyl aryl-ether and trifluoro vinyl p-methoxyphenyl ether is 2:
1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710181054.6A CN106905525B (en) | 2017-03-24 | 2017-03-24 | One kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710181054.6A CN106905525B (en) | 2017-03-24 | 2017-03-24 | One kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106905525A CN106905525A (en) | 2017-06-30 |
| CN106905525B true CN106905525B (en) | 2019-04-30 |
Family
ID=59195144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710181054.6A Active CN106905525B (en) | 2017-03-24 | 2017-03-24 | One kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106905525B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456435B (en) * | 2018-10-09 | 2021-05-11 | 大连理工大学 | Synthetic method of perfluorocyclobutyl polyarylether containing heteronaphthalene biphenyl structure |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210265A (en) * | 1989-06-09 | 1993-05-11 | The Dow Chemical Company | Reactive compounds containing perfluorocyclobutane rings |
| CN104211944B (en) * | 2014-09-25 | 2017-01-18 | 中国科学院上海有机化学研究所 | Multi-fluorine polyarylether, preparation method and application thereof |
| CN104277216B (en) * | 2014-10-08 | 2018-01-30 | 广西大学 | A kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer and its preparation method and application |
-
2017
- 2017-03-24 CN CN201710181054.6A patent/CN106905525B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106905525A (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3423479A (en) | Mixtures of organopolysiloxanes and polyarylene polyethers | |
| CN105601935B (en) | The poly aryl ether ketone polymer of structure containing polysilsesquioxane and preparation method | |
| Saxena et al. | Synthesis and properties of polyarylene ether nitrile copolymers | |
| CN102040737B (en) | PEEK-modified phenol formaldehyde resin and preparation method thereof | |
| CN104725987B (en) | A kind of coating composition and metal material | |
| CN105315454B (en) | The application of the organic-silicon-modified method for preparing siliceous double hydroxyl polyphenylene oxide and product | |
| Liu et al. | Fluorinated poly (aryl ether) containing a 4‐bromophenyl pendant group and its phosphonated derivative | |
| CN106589348A (en) | Polyarylether with main chain containing bisbenzofiurene and triaryl-s-triazine structure and preparation method of polyarylether | |
| Bai et al. | Direct synthesis of fully sulfonated polyarylenethioether sulfones as proton‐conducting polymers for fuel cells | |
| CN101186695A (en) | Soluble fluorine-containing polyaryl ether ketone high-performance material, preparation method thereof and mixed film of the same and epoxy resin | |
| CN106905525B (en) | One kind containing itrile group and perfluorocyclobutanearyl aryl-ether structure poly(aryl ether ketone) and its synthetic method | |
| Pu et al. | Novel low‐dielectric‐constant fluorine‐functionalized polysulfone with outstanding comprehensive properties | |
| CN110240692B (en) | Bio-based flame-retardant furan epoxy resin and preparation method thereof | |
| Dawkins et al. | Polybenzimidazole (PBI) high temperature polymers and blends | |
| CN106947075B (en) | A kind of poly(aryl ether ketone) CABLE MATERIALS resin and its synthetic method | |
| CN113817387B (en) | Polypyrrole/graphene/epoxy resin super-slip coating suitable for photothermal deicing and preparation method thereof | |
| CN106633059B (en) | A kind of acetenyl sealing end poly (arylene ether nitrile) imide resin and preparation method thereof | |
| CN113897025B (en) | Benzoxazine resin-based composition for packaging third-generation semiconductor device and preparation method thereof | |
| CN109851729A (en) | Preparation method of the one kind containing ferrocene/DOPO base and crosslinking alkenyl polyether ether ketone resin | |
| Mesaki et al. | Hybrid composites of polyamide-imide and silica applied to wire insulation | |
| Kern et al. | Poly (arylene ether) s carrying pendant (3‐sulfonated) phenylsulfonyl groups | |
| CN104789112B (en) | High-voltage motor insulating impregnating varnish and preparation method thereof | |
| CN115011240A (en) | High-temperature-resistant and abrasion-resistant paste flame-retardant coating material | |
| Girase et al. | Studies on unsaturated polyester composites for high‐temperature applications | |
| CN109705335A (en) | One kind containing itrile group and DOPO based structures ketone-grouped resin and its synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220407 Address after: 365400 No. 37, Gongye South Road, Chengnan Town, Ninghua County, Sanming City, Fujian Province Patentee after: Fujian Chaoyang wire and cable Co.,Ltd. Address before: 350208 Liyushan Industrial Zone, Heshang Town, Changle City, Fuzhou City, Fujian Province Patentee before: FUZHOU TONGERDA ELECTRIC WIRE & CABLE Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Polyaryl ether ketone containing nitrile and perfluorocyclic butyl aryl ether structures and its synthesis method Effective date of registration: 20230809 Granted publication date: 20190430 Pledgee: Agricultural Bank of China Limited Ninghua County Branch Pledgor: Fujian Chaoyang wire and cable Co.,Ltd. Registration number: Y2023350000179 |