One kind contains itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK and its synthesis
Method
Technical field
Contain itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK and its synthetic method the present invention relates to one kind, belong to
Polymeric material field.
Background technology
As the scope of power cable application is more and more wider, different use environments have different requirements, e.g., high temperature resistant, resistance to low
Temperature, oil resistant, tear-proof, fire-retardant etc..Particularly use condition is special, applied environment it is complicated in the case of, the need of special cable
Day aobvious protrusion is sought, reliability, durability to cable propose requirement higher.China Express Railway and urban track traffic are filled
Standby to quickly grow, requirement of the manufacturing enterprise to high ferro and urban rail dress cable in stock is towards ultra-thin-wall, high-temperature resistant, oil resistant high, high resistant
Combustion direction is developed.The insulating wall thickness of common thin-walled cable is in more than 0.3mm, and high-speed railway and urban track traffic equipment institute
The ultra-thin-wall insulated cable insulation wall thickness requirement for needing is 0.18mm.At present, cable industry produces the primary insulation material of thin-walled cable
Material is cross-linked polyolefin, and due to containing more fire retardant in the CABLE MATERIALS, insulaion resistance is smaller, and cable is easily breakdown, and
And the physical and mechanical properties of cable has many deficiencies, insulation wall can not be realized ultra-thin, it is difficult to the need for meeting manufacturing enterprise.Cause
This, production high-temperature resistant, oil resistant high, a key technology of the ultra-thin-wall insulated cable of high fire-retardance are exactly to study suitable cable
Material.
PAEK is a kind of aromatics thermoplastic special engineering plastic, with 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, with intensity is higher, high abrasion, oil resistant high, electrical insulating property
It is good, and with the characteristic such as low cigarette, Halogen, fire-retardant, it is adapted to electricity thin-walled cable extrusion.CN105542390A provides a kind of resistance to thermal resistance
Combustion cable insulation material, by polyether-ether-ketone, chlorinated paraffin, alkyd resin, Lauxite, blanc fixe, asbestos, five bromoethyls
Benzene, mica powder, low density polyethylene (LDPE), calcinated argil, palm oil, glycerine, 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 compounding is formed, and adding a small amount of retardant synergist just makes the 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.And for example, patent CN105400131A provides a kind of special cable with again
Condensation material, the special cable composite is made up of following component:Polyether-ether-ketone, polyethylene, polyimides mix in proportion
As matrix material, using ethene-vinyl acetate copolymer is polymer-modified, molybdenum trioxide, magnesia are after coupling agent treatment
As flame-retardant additive, using cumyl peroxide as crosslinking catalyst, using silicon nitride crystal whisker as reinforcing agent, pass through
Melt blending forms composite, and it has preferable high temperature resistant property and the flame retardant effect for improving, and can realize bad working environments
Under stability do not reduce.However, formation homogeneous blend is more difficult between above-mentioned polymer, it is more multiple to preparation technology requirement
It is miscellaneous, and the auxiliary agent of its addition is more, undoubtedly increased product cost, reduces the reliability of cable.It can be seen that, it is existing to overcome
Many defects in technology, need a kind of high temperature resistant, reliability fire-retardant, that shielding system energy is good novel cable material high badly.
Make the electric wire that insulation and sheath material are made with fluoroplastics (such as polytetrafluoroethylene (PTFE), perfluoroethylene-propylene),
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 produced under similarity condition is more much smaller than PVC material;Its combustion product is to equipment, instrument
The corrosivity of device is lower than PE, PVC material.In addition, its dielectric constant, dielectric dissipation factor, the letter of High Speed Transfer frequency band
The electric wire of number attenuation ratio other materials is all small, and physical and mechanical properties is better than other materials.
Poly (arylene ether nitrile) is the high performance engineering plastics that a class contains cyano group side base, with excellent high temperature resistant, corrosion-resistant, resistance to
Radiation, fire-retardant, physical and mechanical properties and fabulous dimensional stability in a balanced way.Due to drawing for highly polar cyano group side base (- CN)
Enter, on the one hand increased the dipole-dipole effect of molecule interchain, be conducive to obtaining heat resistance higher and mechanical strength
Meanwhile, the adhesive force of reinforced resin matrix;On the other hand, cyano group can be formed with higher resistance to as a potential crosslinking points
The network structure of hot property.
In sum, be incorporated into PAEK main chain for cyano group and perfluorocyclobutanearyl aryl-ether structure and prepare by the applicant
Cyano-containing and perfluorocyclobutanearyl aryl-ether structure PAEK so that the resinoid have simultaneously poly (arylene ether nitrile), polyether-ether-ketone and
The advantage of fluoroplastics.
The content of the invention
In order to solve the above mentioned problem existing for prior art, itrile group and perfluorocyclobutanearyl are contained the invention provides one kind
Aryl ether structures PAEK and its synthetic method, perfluorocyclobutanearyl aryl-ether structure PAEK prepared by the method have good
Good heat endurance and chemical stability.
Technical scheme is as follows:
Contain itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK the present invention relates to one kind, structural formula is as follows:
M represents the degree of polymerization, is positive integer.
Wherein, 1≤m≤200.
Wherein, 10≤X+Y≤50.
Additionally, the invention also discloses a kind of synthesis side containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK
Method, comprises the following steps:By perfluorocyclobutanearyl aryl-ether phenol polymer, phenyl-dihalide formonitrile HCN or dihalo para-Phthalonitrile, 4,
4 '-difluoro benzophenone is in molar ratio 1 with catalyst:(1~0.1):(0.1~1):(2~3) are placed in organic solvent and toluene
Mixed solvent in, in N2Under stream effect, after carrying out temperature control reaction twice, reaction solution is poured into deionized water under agitation immediately
Middle precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water is changed once every 2~5h, is filtered after 24h, will
Sediment is placed in 80 DEG C of vacuum drying ovens and dries 10h, obtains containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK sample
Product.
Wherein, the temperature control twice reaction be prior to 130~150 DEG C of 1~5h of reaction, then at 150~170 DEG C of reactions 3~
10h。
Wherein, described phenyl-dihalide formonitrile HCN uses 2,5- dichlorobenzonitriles or 2,5- difluorobenzonitrile;The dihalo
Para-Phthalonitrile is 2,5- dichloros para-Phthalonitrile or 2,5- dibromo para-Phthalonitriles.
Wherein, the organic solvent uses DMA, dimethyl sulfoxide or 1-METHYLPYRROLIDONE.
Wherein, the catalyst uses Anhydrous potassium carbonate or natrium carbonicum calcinatum.
Wherein, perfluorocyclobutanearyl aryl-ether phenol polymer synthesis comprises the following steps:Trifluorovinyl Aryl Ethers are dissolved
In diphenyl ether, it is placed in 160 DEG C of oil baths after polyase 13 h, obtains product for perfluorocyclobutanearyl aryl-ether monomer, adds trifluoro second
Alkenyl p-methoxyphenyl ether continues to react 7h as end-capping reagent, and terminating reaction obtains the perfluor ring fourth for containing methoxyl group in end
Base aryl ether polymer, by with BBr3Reaction demethylation obtains end for hydroxyl contains the polymerization of perfluorocyclobutanearyl aryl-ether phenol
Thing.
Wherein, the perfluorocyclobutanearyl aryl-ether is with a mole molar ratio for trifluoro vinyl p-methoxyphenyl ether
2∶1。
The present invention has the advantages that:
1st, the present invention synthesizes a kind of containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK first, develops one kind
Novel cable material.
2nd, one kind of present invention synthesis contains itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK, while having poly- virtue
The advantage of ether nitrile, polyether-ether-ketone and fluoroplastics.
3rd, the present invention is a kind of contains itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK, and the material has compared with high temperature resistant
Decay resistance, radiation hardness, fire resistance, with more crosslinking points.
4th, the present invention is a kind of contains itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK, the material dielectric constant, Jie
Matter loss factor, High Speed Transfer frequency band signal attenuation it is smaller than the electric wire of commercially available material, physical and mechanical properties is also substantially carried
It is high.
5th, a kind of synthetic method containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK of the present invention, the synthesis side
Method is simple, and synthetic yield is higher, low production cost.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention 2 obtain it is infrared containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK
Spectrogram;
Fig. 2 is the IH- containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK that the embodiment of the present invention 2 is obtained
NMR spectra.
Specific embodiment
The following is several embodiments of the present invention, the present invention is further illustrated, 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, product is obtained for perfluorocyclobutanearyl aryl-ether monomer, add trifluoro vinyl p-methoxyphenyl
Used as end agent, (monomer is 2 with the molar ratio of end-capping reagent to ether envelope:1), continue to react 7h, terminating reaction obtains end and contains
The perfluorocyclobutanearyl aryl-ether polymer of methoxyl group, by with BBr3Reaction demethylation obtains end and contains perfluor ring fourth for hydroxyl
Base aryl ether phenol polymer, by gpc analysis:Mn=2450, PDI=1.25.Its synthetic route:
Embodiment 1
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK:Sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ethers phenol polymer, 0.69g (4mmol) 2,5- dichlorobenzonitriles, 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 deionized water reaction solution under agitation
Precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water was changed once every 3 hours, is filtered after 24 hours,
Put the precipitate in 80 DEG C of vacuum drying ovens and dry 10 hours, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis:Mn=53339, PDI=2.85, yield are 96%.Its synthetic route:
Embodiment 2
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK:Sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ethers phenol polymer, 1.03g (6mmol) 2,5- dichlorobenzonitriles, 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 deionized water reaction solution under agitation
Precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water was changed once every 3 hours, is filtered after 24 hours,
Put the precipitate in 80 DEG C of vacuum drying ovens and dry 10 hours, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis:Mn=54436, PDI=2.95, yield are 97.5%, and are shown by DSC results of study, this reality
The glass transition temperature for applying the PAEK sample of example preparation is 175 DEG C, is shown by thermal gravimetric analysis results, synthesized sample
Initial weightless temperature is 450 DEG C, and weightless 5% temperature is 467 DEG C.Additionally, viscosity test also is carried out to prepared sample, will
It is dissolved in DMF at 25 DEG C containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK sample, determines its viscosity, as a result table
Bright 0.26dL/g.
Embodiment 3
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK:Sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ethers phenol polymer, 1.37g (8mmol) 2,5- dichlorobenzonitriles, 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 deionized water reaction solution under agitation
Precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water was changed once every 3 hours, is filtered after 24 hours,
Put the precipitate in 80 DEG C of vacuum drying ovens and dry 10 hours, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis:Mn=52478, PDI=2.75, yield are 96.5%.
Embodiment 4
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK:Sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ethers phenol polymer, 1.72g (10mmol) 2,5- dichlorobenzonitriles, 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 deionized water reaction solution under agitation
Precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water was changed once every 3 hours, is filtered after 24 hours,
Put the precipitate in 80 DEG C of vacuum drying ovens and dry 10 hours, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis:Mn=51432, PDI=2.82, yield are 95.3%.
Embodiment 5
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK:Sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ethers phenol polymer, 0.83g (6mmol) 2,5- difluorobenzonitriles, 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 deionized water reaction solution under agitation
Precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water was changed once every 3 hours, is filtered after 24 hours,
Put the precipitate in 80 DEG C of vacuum drying ovens and dry 10 hours, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis:Mn=54345, PDI=2.85, yield are 97%.Its synthetic route:
Embodiment 6
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK:Sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ethers phenol polymer, 1.18g (6mmol) 2,5- dichloros 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 deionized water reaction solution under agitation
Precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water was changed once every 3 hours, is filtered after 24 hours,
Put the precipitate in 80 DEG C of vacuum drying ovens and dry 10 hours, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis:Mn=55647, PDI=2.79, yield are 97.5%.Its synthetic route:
Embodiment 7
Synthesis containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK:Sequentially added in conical flask
49.0000g (20mmol) perfluorocyclobutanearyl aryl-ethers phenol polymer, 0.98g (6mmol) 2,5- difluoros 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 deionized water reaction solution under agitation
Precipitation, filtering.The sediment that will be filtrated to get is soaked with deionized water, and water was changed once every 3 hours, is filtered after 24 hours,
Put the precipitate in 80 DEG C of vacuum drying ovens and dry 10 hours, obtain containing itrile group and perfluorocyclobutanearyl aryl-ether structure polyarylether
Ketone sample passes through gpc analysis:Mn=54943, PDI=2.78, yield are 97.8%.Its synthetic route:
Fig. 1 is the infrared spectrogram containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK 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 bonds characteristic absorption peak on phenyl ring,
1234cm-1There is Ar-O-Ar specific peak absorbances peak, 2217cm-1There is the characteristic absorption peak of-CN, illustrate difluoro cyano group benzene, two
Fluorine benzophenone reacts with hexafluoro bisphenol-a, preliminary accordingly to infer that product is to contain itrile group and perfluorocyclobutanearyl aryl-ether structure
PAEK.
Fig. 2 is the IH- containing itrile group and perfluorocyclobutanearyl aryl-ether structure PAEK that the embodiment of the present invention 2 is obtained
NMR spectra.δ 7.85,7.83,7.79,7.78,7.76,7.73 and δ 7.42,7.14,7.23,7.22 is cyano group 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 is proton on phenyl ring in phenol monomer
Peak.
And Mn=53345 is changed into from perfluorocyclobutanearyl aryl-ether phenol Mn=2450 by gpc analysis, synthetic point
Son amount increases.Provable perfluorocyclobutanearyl aryl-ether phenol, difluoro cyano group benzene and difluoro benzophenone there occurs polycondensation reaction, success
Itrile group and perfluorocyclobutanearyl aryl-ether are incorporated into PAEK main chain, synthesized linear containing itrile group and perfluorocyclobutanearyl
The PAEK of aryl ether structures.
Embodiments of the invention are the foregoing is only, the scope of the claims of the invention is not thereby limited, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.