CN109880078A - A kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone and preparation method thereof - Google Patents
A kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone and preparation method thereof Download PDFInfo
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- CN109880078A CN109880078A CN201811642170.4A CN201811642170A CN109880078A CN 109880078 A CN109880078 A CN 109880078A CN 201811642170 A CN201811642170 A CN 201811642170A CN 109880078 A CN109880078 A CN 109880078A
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Abstract
The invention discloses a kind of preparation methods of thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone.This method is by three component biphenol monomers, difluoro benzophenone, K2CO3Or Na2CO3It is placed in organic solvent for 1:1:1.2~2.0 in molar ratio, in N2Prior to 130~150 DEG C 1~5h of reaction prepare thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone then at 150~170 DEG C of 3~20h of reaction under stream effect.This method is simple and easy to do, prepares thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone using gradually polymerization.The CABLE MATERIALS made of the present invention,, high abrasion higher with intensity, high oil resistant, high temperature resistant, radiation hardness, electrical insulating property are good, and there are the characteristics such as low cigarette, Halogen, fire-retardant, it is very suitable to ultra-thin-wall cable extrusion, it is able to satisfy the processing technology and product technology requirement of ultra-thin-wall insulated cable, it is convenient for production, with good economic efficiency and promotional value.
Description
Technical field
The present invention relates to a kind of polyether-ether-ketone technical fields, and in particular to a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material
Polyether-ether-ketone extremely preparation method.
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 material contain more fire retardant, insulation resistance is smaller, cable be easy it is breakdown,
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.
Therefore, produce 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.
Organic phosphorus flame retardant has many advantages, such as efficient, less toxic, pollution-free, low cigarette, receive more and more attention, but
It is often along with the decline of material mechanical performance, and to go out to gather with easy to migrate in the form of DOPO small molecule in direct added material
Object material is closed, its flame retardant property is influenced.Aggretion type organic phosphine fire retardant includes that molecular weight is big, phosphorus content is high, compatible with material
The advantages that property is good, migration is small, processing performance is good, excellent fireproof performance.Considered based on above-mentioned advantage, by the fire-retardant class agent of organic phosphine
Polymerization reaction is directly participated in monomeric form, as a part of structural unit in main polymer chain, to make polymer material
Reach fire-retardant purpose.It also solves the compatibility of fire retardant and substrate during use, dispersibility, interface characteristics etc. simultaneously to ask
Topic.Ferrocene is a kind of iron content organo-metallic compound, is similar to phenyl ring, chemical property is more active, and it is anti-to can be carried out parental materials
It answers.Ferrocene and its derivative is widely used in the multiple fields such as electrochemistry, biomedicine, catalysis, magnetic material and liquid crystal；Two
Luxuriant iron thermal stability is high, and decomposition temperature is 454 DEG C, and ferrocene is decomposed into cyclopentadiene and iron when heated, and iron atom has excellent
Catalysis carbon-forming effect, energy conservation, eliminate smoke and at charcoal in terms of have important role.
Polyether-ether-ketone is a kind of high performance engineering plastics, with excellent high temperature resistant, corrosion-resistant, radiation hardness, equilibrium object
Manage mechanical performance and fabulous dimensional stability.DOPO base bis-phenol structural unit will be contained and introduce polyethers ether containing ferrocene monomer
In ketone main chain prepare the polyether-ether-ketone of based structures containing DOPO new varieties, the resinoid have simultaneously polyether-ether-ketone high temperature resistant, it is corrosion-resistant,
Radiation hardness and the advantages of DOPO is fire-retardant and ferrocene promotion is acted at charcoal.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, provides a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material
Polyether-ether-ketone extremely preparation method.
The principle of the present invention is as described below: using weak base such as potassium carbonate or sodium carbonate at salt, DOPO base being introduced polyethers ether
Thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone is prepared in ketone side group, and there is intensity height, high temperature resistant, radiation hardness, height
Wear-resisting, high oil resistant, electrical insulating property are good, and have the characteristics such as low cigarette, Halogen, fire-retardant, are very suitable to ultra-thin-wall cable extrusion, can be full
Processing technology and the product technology requirement of sufficient ultra-thin-wall insulated cable, convenient for production, with good economic efficiency and promotion price
Value.
The present invention is achieved through the following technical solutions:
(1) a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone, it is characterised in that structure are as follows:
R in formula are as follows:
(2) preparation method of polyether-ether-ketone
By three component biphenol monomers, difluoro benzophenone, catalyst I, 1:1:1.2~2.0 are placed in organic solvent I in molar ratio
In, in N2It is resistance to prepare thin-walled then at 150~170 DEG C of 3~20h of reaction by prior to 130~150 DEG C 1~5h of reaction under airflow function
High temperature radiation hardness fire-resistant cable material polyether-ether-ketone.
The three component biphenol monomers are the biphenol monomer of substituent group containing DOPO, contain ferrocene and DOPO base bis-phenol list
Body and appointing in hydroquinone, resorcinol, bisphenol fluorene, bisphenol-A, hexafluoro bisphenol-a, '-biphenyl diphenol, O-methoxy hydroquinone
The combination of one kind of anticipating.
Described is as follows containing ferrocene and DOPO base biphenol monomer, preparation method:
DOPO base trihydric phenol will be contained, triethylamine is added in organic solvent II, by two formyl of ferrocene under being stirred in ice-water bath
Chlorine instills in above-mentioned solution, is reacted for 24 hours at room temperature, solvent is evaporated off, cool down, be filtered, washed, dry, obtain containing ferrocene with
DOPO base biphenol monomer.
Or: DOPO base trihydric phenol, ferrocenecarboxylic acid and 4-dimethylaminopyridine will be contained and be added in organic solvent II, in nitrogen
Under protection, after stirring 30min, by N, N'- Dicyclohexylcarbodiimide dichloromethane solution is added dropwise in above-mentioned solution, under stirring
And warm naturally to room temperature the reaction was continued for 24 hours, reaction solution is concentrated, cool down, be filtered, washed, is dried, obtain containing ferrocene and
DOPO base biphenol monomer.
The biphenol monomer preparation step of substituent group containing DOPO is as follows:
Parahydroxyben-zaldehyde and diamino compounds are added in organic solvent III with 2:1 molar ratio feed ratio, nitrogen is protected
React 2h at 20~50 DEG C in shield, be subsequently added into the DOPO of diamino compounds equimolar amounts the reaction was continued for 24 hours, terminate anti-
It answers, obtains the biphenol monomer of substituent group containing DOPO.
Wherein, the diamino compounds in step are 2,4- diaminotoluene, p-phenylenediamine, m-phenylene diamine (MPD), join adjacent toluene
Diamines, 4,4 '-diaminodiphenyl ethers, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfides, 4,4 '-diamino two
Benzophenone, 4,4 '-diamino octafluorobiphenyls, 1,3- bis- (4- phenalgin oxygroup) benzene, 4,4 '-two (4- amino-benzene oxygen) biphenyl, 4,
4 '-bis- (3- amino-benzene oxygen) benzophenone, 4,4 '-diamino -2,2 '-dimethyl -1, any one in 1 '-biphenyl.
Wherein, organic solvent I described in step is toluene and n,N-dimethylacetamide, dimethyl sulfoxide, N- methyl pyrrole
Any one or any two kinds of combination of pyrrolidone.Organic solvent II is methylene chloride, 1,2- dichloroethanes, chloroform, tetrachloro
Methane, toluene any one.Organic solvent III is dehydrated alcohol, anhydrous methanol, ethyl acetate, tetrahydrofuran, acetone, dioxy six
Any one in ring, carbon tetrachloride.
Wherein, catalyst I described in step is Anhydrous potassium carbonate or natrium carbonicum calcinatum.
Compared with the existing technology, the invention has the advantages that and the utility model has the advantages that
1. the present invention will prepare polyethers ether by polycondensation reaction containing DOPO substituent group biphenol monomer, containing ferrocene monomer
Ketone, this method weak base is at salt, and having overcome industrial, use NaOH is degradable at product caused by salt, it is dirty to react difficult to control and alkali
High molecular weight thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone, the equal average molecular of polymer number is made in the problems such as dye
Quality is between 1.5-10 ten thousand.
2. containing P-C key in thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone structure, more stable, bond energy is very
By force, it can just be broken at very high temperatures, still be able to maintain it after introducing DOPO base bis-phenol structural unit in polyether-ether-ketone main chain
High temperature resistance, thus such stability of material is good, flame retardant property is more longlasting, to meet the needs of higher level application.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, but it is noted that following embodiment should not be understood as
Limiting the scope of the invention, those skilled in the art's above content according to the present invention make the present invention some
Nonessential modifications and adaptations still fall within protection scope of the present invention.
Embodiment 1
(1)) base containing DOPO three preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
First phenol 2.9041g, ferrocenecarboxylic acid 2.3004g, 4-dimethylaminopyridine 2.4534g and methylene chloride 120mL, and put it into
Stirring and fill N2 gas in ice bath, by 2.0830g N after 30min, N'- Dicyclohexylcarbodiimide is dissolved in 10mL methylene chloride,
Be added dropwise in 60min in above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, by reaction solution concentration, it is cold
But, it is filtered, washed, dries, put the precipitate in dry 10h in 40 DEG C of vacuum drying ovens, obtains double containing ferrocene and DOPO base
Phenol monomer.
(2) preparation of DOPO substituent group biphenol monomer (I): in single port bottle be added 6.1060g parahydroxyben-zaldehyde,
4,4 '-diaminodiphenylmethane of 4.9565g and 90mL ethyl acetate, stir evenly, react 2h at 40 DEG C in nitrogen atmosphere, then
The reaction was continued by addition 10.8085g DOPO for 24 hours, terminates reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids
It impregnated, elution, filtered with ethyl alcohol, be dried in vacuo at 60 DEG C for 24 hours, obtain the biphenol monomer of substituent group containing DOPO (I).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO substituent group biphenol monomer (I) 1.6777g (2mmol), containing ferrocene and DOPO base biphenol monomer 0.5020g (1mmol),
Hexafluoro bisphenol-a 5.7159g (17mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL,
1mL/ seconds N2 flow down 140 DEG C and react 3 hours, then heat to 170 DEG C of reactions 10 hours, under stiring by reaction solution immediately
It pours into deionized water and precipitates, filter.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, puts the precipitate in drying 10 hours in 80 DEG C of vacuum drying ovens, obtain the fire-retardant electricity of thin-walled high temperature resistant radiation hardness
Cable material-polyether-ether-ketone.
Embodiment 2
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) preparation of the biphenol monomer of substituent group containing DOPO (II): in single port bottle be added 6.1060g parahydroxyben-zaldehyde,
2.7035g p-phenylenediamine and 90mL dehydrated alcohol, stir evenly, and react 2h at 40 DEG C in nitrogen atmosphere, are subsequently added into 10.8085g
The reaction was continued by DOPO for 24 hours, terminates reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids impregnates with ethyl alcohol, leaching
It washes, filter, be dried in vacuo at 60 DEG C for 24 hours, obtain the biphenol monomer of substituent group containing DOPO (II).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (II) 2.9950g (4mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), bisphenol-A
3.4260g (15mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL were flowed in 1mL/ seconds N2
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 7 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, thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyethers ether is obtained
Ketone.
Embodiment 3
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) preparation of the biphenol monomer of substituent group containing DOPO (III): in single port bottle be added 6.1060g parahydroxyben-zaldehyde,
5.0060g4,4 '-diaminodiphenyl ethers and 100mL ethyl acetate, stir evenly, and react 2h in nitrogen atmosphere at 50 DEG C, then plus
Enter 10.8085g DOPO the reaction was continued for 24 hours, terminates reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids is used
Ethyl alcohol is impregnated, elution, is filtered, and is dried in vacuo for 24 hours at 60 DEG C, is obtained the biphenol monomer of substituent group containing DOPO (III).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (III) 0.8408g (1mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), hexafluoro pair
Phenol A 6.0521g (18mmol), difluoro benzophenone 4.3640g (20 mmol), toluene 100mL, DMAc120mL, at 1mL/ seconds
N2 flow down 140 DEG C react 3 hours, then heat to 170 DEG C react 15 hours, reaction solution is poured under stiring immediately from
It precipitates, filters in sub- water.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, 24 hours
After filter, put the precipitate in 80 DEG C of vacuum drying ovens 10 hours dry, obtain thin-walled high temperature resistant radiation hardness fire-resistant cable material-
Polyether-ether-ketone.
Embodiment 4
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) preparation of the biphenol monomer of substituent group containing DOPO (III): in single port bottle be added 6.1060g parahydroxyben-zaldehyde,
5.0060g4,4 '-diaminodiphenyl ethers and 100mL ethyl acetate, stir evenly, and react 2h in nitrogen atmosphere at 50 DEG C, then plus
Enter 10.8085g DOPO the reaction was continued for 24 hours, terminates reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids is used
Ethyl alcohol is impregnated, elution, is filtered, and is dried in vacuo for 24 hours at 60 DEG C, is obtained the biphenol monomer of substituent group containing DOPO (III).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (III) 1.6816g (2mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), isophthalic two
Phenol 1.3212g (12mmol), difluoro benzophenone 3.2730g (15mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2
It flows down 140 DEG C to react 3 hours, then heats to 170 DEG C and react 7 hours, reaction solution is poured into deionized water under stiring immediately
Middle precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, 24 hour after mistake primary every 3 hours replacement water
Filter puts the precipitate in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyethers
Ether ketone.
Embodiment 5
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) preparation of the biphenol monomer of substituent group containing DOPO (IV): in single port bottle be added 6.1060g parahydroxyben-zaldehyde,
4,4 '-diaminobenzophenone of 5.3063g and 100mL tetrahydrofuran, stir evenly, react 2h at 50 DEG C in nitrogen atmosphere, then
The reaction was continued by addition 10.8085g DOPO for 24 hours, terminates reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids
It impregnated, elution, filtered with ethyl alcohol, be dried in vacuo at 60 DEG C for 24 hours, obtain the biphenol monomer of substituent group containing DOPO (IV).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (IV) 3.4113g (4mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), biphenyl two
Phenol 2.7932g (15mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2
It flows down 140 DEG C to react 3 hours, then heats to 170 DEG C and react 15 hours, reaction solution is poured into deionized water under stiring immediately
Middle precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, 24 hour after mistake primary every 3 hours replacement water
Filter puts the precipitate in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyethers ether
Ketone.
Embodiment 6
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) preparation of the biphenol monomer of substituent group containing DOPO (V): in single port bottle be added 6.1060g parahydroxyben-zaldehyde,
4,4 '-diamino octafluorobiphenyl of 8.2045g and 120mL tetrahydro carbon, stir evenly, react 2h at 50 DEG C in nitrogen atmosphere, then
The reaction was continued by addition 10.8085g DOPO for 24 hours, terminates reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids
It impregnated, elution, filtered with ethyl alcohol, be dried in vacuo at 60 DEG C for 24 hours, obtain the biphenol monomer of substituent group containing DOPO (V).
。
(3) thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially added in three-necked flask containing
The bis-phenol of base containing DOPO (V) 3.8752g (4mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), hexafluoro
Bisphenol-A 3.3623g (10mmol), difluoro benzophenone 3.2730g (15 mmol), toluene 80mL, DMAc100mL, in 1mL/
The N2 of second flows down 140 DEG C and reacts 3 hours, then heats to 170 DEG C and reacts 10 hours, immediately pours into reaction solution under stiring
It precipitates, filters in ionized water.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, 24 hours
After filter, put the precipitate in 80 DEG C of vacuum drying ovens 10 hours dry, it is poly- to obtain thin-walled high temperature resistant radiation hardness fire-resistant cable material-
Ether ether ketone.
Embodiment 7
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) 6.1060g parahydroxyben-zaldehyde, 5.0060g4,4 '-diaminodiphenyl ether and 100mL are added in single port bottle
Ethyl acetate stirs evenly, and reacts 2h at 50 DEG C in nitrogen atmosphere, is subsequently added into 10.8085g DOPO the reaction was continued for 24 hours, terminate
Reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids is impregnated with ethyl alcohol, elution, filtered, the vacuum at 60 DEG C
Drying for 24 hours, obtains the biphenol monomer of substituent group containing DOPO (III).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (III) 2.5225g (3mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), isophthalic two
Phenol 1.1101g (10mmol), difluoro benzophenone 3.0548g (14mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2
It flows down 140 DEG C to react 3 hours, then heats to 170 DEG C and react 20 hours, reaction solution is poured into deionized water under stiring immediately
Middle precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, 24 hour after mistake primary every 3 hours replacement water
Filter puts the precipitate in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyethers ether
Ketone.
Embodiment 8
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) in single port bottle be added 6.1060g parahydroxyben-zaldehyde, 8.2045g 4,4 '-diamino octafluorobiphenyl and
120mL tetrahydro carbon, stirs evenly, and reacts 2h at 50 DEG C in nitrogen atmosphere, is subsequently added into 10.8085g DOPO the reaction was continued for 24 hours,
Reaction is terminated,.Reaction solution is cooled to room temperature, the solid was filtered object, solids is impregnated with ethyl alcohol, elution, filtered, at 60 DEG C
Vacuum drying for 24 hours, obtains the biphenol monomer of substituent group containing DOPO (V).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (V) 3.8752g (4mmol) contains ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), hydroquinone
1.6515g (15mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL were flowed in 1mL/ seconds N2
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, thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyethers ether is obtained
Ketone.
Embodiment 9
(1) ternary of base containing DOPO the preparation containing ferrocene and DOPO base biphenol monomer: is sequentially added in three-necked flask
Phenol 2.9041g, triethylamine 2.0326g and methylene chloride 120mL, and put it into ice bath after stirring 30min, by ferrocene first
Acyl chlorides 2.4754g, which is dissolved in methylene chloride, instills above-mentioned solution, warmed naturally under stirring room temperature and the reaction was continued for 24 hours, will be anti-
It answers liquid to be concentrated, cool down, be filtered, washed, drying, puts the precipitate in dry 5h in 40 DEG C of vacuum drying ovens, obtain containing ferrocene
With DOPO base biphenol monomer.
(2) 6.1060g parahydroxyben-zaldehyde, 2.7035g p-phenylenediamine and 90mL dehydrated alcohol are added in single port bottle, stirs
It mixes uniformly, reacts 2h at 40 DEG C in nitrogen atmosphere, be subsequently added into 10.8085g DOPO the reaction was continued for 24 hours, terminate reaction,.It will reaction
Liquid is cooled to room temperature, the solid was filtered object, solids are impregnated with ethyl alcohol, elution, are filtered, be dried in vacuo for 24 hours, obtain at 60 DEG C
The biphenol monomer of substituent group containing DOPO (II).
(3) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (II) 1.4975g (2mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), bisphenol fluorene
5.9571g (17mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL were flowed in 1mL/ seconds N2
Lower 140 DEG C are reacted 3 hours, are then heated to 170 DEG C and are reacted 7 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, thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone is obtained.
Embodiment 10
The preparation of thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone: it sequentially adds in three-necked flask containing DOPO
Base bis-phenol (II) 0.7488g (1mmol), contain ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), bisphenol fluorene
6.3075g (18mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2
It flows down 140 DEG C to react 3 hours, then heats to 170 DEG C and react 7 hours, reaction solution is poured into deionized water under stiring immediately
Middle precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, 24 hour after mistake primary every 3 hours replacement water
Filter puts the precipitate in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyethers
Ether ketone.
Embodiment 11
(1) 6.1060g parahydroxyben-zaldehyde, 9.2108g 4,4 '-two (4- amino-benzene oxygen) connection are added in single port bottle
Benzene and 120mL 1,2- dichloroethanes stir evenly, and react 2h at 50 DEG C in nitrogen atmosphere, be subsequently added into 10.8085g DOPO after
Continuous reaction for 24 hours, terminates reaction,.Reaction solution is cooled to room temperature, the solid was filtered object, solids is impregnated with ethyl alcohol, elution, taken out
Filter, is dried in vacuo for 24 hours at 60 DEG C, obtains the biphenol monomer of substituent group containing DOPO (VI).
(2) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (VI) 2.3940g (2mmol) contains ferrocene and DOPO base biphenol monomer 0.5020g (1mmol), to benzene two
Phenol 1.8717g (17mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2
It flows down 140 DEG C to react 3 hours, then heats to 170 DEG C and react 20 hours, reaction solution is poured into deionized water under stiring immediately
Middle precipitating, filtering.The sediment being obtained by filtration is impregnated with deionized water, 24 hour after mistake primary every 3 hours replacement water
Filter puts the precipitate in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyethers ether
Ketone.
Embodiment 12
(1) 6.1060g parahydroxyben-zaldehyde, 7.3083g 1,3- bis- (4- amino-benzene oxygen) benzene are added in single port bottle
It with 150mL tetrahydrofuran, stirs evenly, reacts 2h at 50 DEG C in nitrogen atmosphere, being subsequently added into 10.8085g DOPO, the reaction was continued
For 24 hours, reaction is terminated,.Reaction solution is cooled to room temperature, the solid was filtered object, solids is impregnated with ethyl alcohol, elution, filtered, 60
It is dried in vacuo at DEG C for 24 hours, obtains the biphenol monomer of substituent group containing DOPO (VII).
(2) it thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone preparation: sequentially adds and contains in three-necked flask
DOPO base bis-phenol (VII) is warming up to 170 DEG C and reacts 20 hours, pours into deionized water reaction solution under stiring precipitate immediately, mistake
Filter.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it filters, will precipitate after 24 hours
Object is placed in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains thin-walled high temperature resistant radiation hardness fire-resistant cable material-polyether-ether-ketone.
Claims (10)
1. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone, it is characterised in that structural formula are as follows:
R in formula are as follows:
2. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone and preparation method thereof, it is characterised in that three components are double
1:1:1.2~2.0 are placed in organic solvent I in molar ratio for phenol monomer, difluoro benzophenone, catalyst I, in N2Under airflow function first
Thin-walled high temperature resistant radiation hardness fire-resistant cable material is prepared then at 150~170 DEG C of 3~20h of reaction in 130~150 DEG C of 1~5h of reaction
Polyether-ether-ketone.
3. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 2 and preparation method thereof,
It is characterized in that the three component biphenol monomers are the biphenol monomer of substituent group containing DOPO, contain ferrocene and DOPO base bis-phenol list
Body and appointing in hydroquinone, resorcinol, bisphenol fluorene, bisphenol-A, hexafluoro bisphenol-a, '-biphenyl diphenol, O-methoxy hydroquinone
The combination of one kind of anticipating.
4. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 2 and preparation method thereof,
It is characterized in that described is as follows containing ferrocene and DOPO base biphenol monomer, preparation method:
To contain DOPO base trihydric phenol, triethylamine be added organic solvent II in, in ice-water bath stir under ferrocene dimethyl chloride is dripped
Enter in above-mentioned solution, react at room temperature for 24 hours, solvent is evaporated off, cool down, be filtered, washed, dry, obtains containing ferrocene and DOPO base
Biphenol monomer；
Or: DOPO base trihydric phenol, ferrocenecarboxylic acid and 4-dimethylaminopyridine will be contained and be added in organic solvent II, in nitrogen protection
Under, after stirring 30min, by N, N'- Dicyclohexylcarbodiimide dichloromethane solution is added dropwise in above-mentioned solution, under stirring and certainly
It is so warming up to room temperature the reaction was continued for 24 hours, reaction solution is concentrated, cool down, be filtered, washed, is dried, is obtained containing ferrocene and DOPO base
Biphenol monomer.
5. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 2 and preparation method thereof,
It is characterized in that the biphenol monomer preparation step of substituent group containing DOPO is as follows:
Parahydroxyben-zaldehyde and diamino compounds are added in organic solvent III with 2:1 molar ratio feed ratio, in nitrogen protection
React 2h at 20~50 DEG C, be subsequently added into the DOPO of diamino compounds equimolar amounts the reaction was continued for 24 hours, terminate reaction, obtain
To the biphenol monomer of substituent group containing DOPO.
6. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 5 and preparation method thereof,
It is characterized in that wherein, the diamino compounds in step are 2,4- diaminotoluene, p-phenylenediamine, m-phenylene diamine (MPD), join adjacent first
Phenylenediamine, 4,4 '-diaminodiphenyl ethers, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl sulfides, 4,4 '-diamino
Benzophenone, 4,4 '-diamino octafluorobiphenyls, 1,3- bis- (4- phenalgin oxygroup) benzene, 4,4 '-two (4- amino-benzene oxygen) biphenyl,
4,4 '-bis- (3- amino-benzene oxygen) benzophenone, 4,4 '-diamino -2,2 '-dimethyl -1, any one in 1 '-biphenyl.
7. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 2 and preparation method thereof,
It is characterized in that the organic solvent I is times of toluene and n,N-dimethylacetamide, dimethyl sulfoxide, N-Methyl pyrrolidone
One kind of anticipating or any two kinds of combination.
8. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 2 and preparation method thereof,
It is characterized in that the catalyst I is Anhydrous potassium carbonate or natrium carbonicum calcinatum.
9. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 4 and preparation method thereof,
It is characterized in that the organic solvent II be methylene chloride, 1,2- dichloroethanes, chloroform, tetrachloromethane, toluene any one.
10. a kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone according to claim 4 and preparation method thereof,
It is characterized in that the organic solvent III is dehydrated alcohol, anhydrous methanol, ethyl acetate, tetrahydrofuran, acetone, dioxy six
Any one in ring, carbon tetrachloride.
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