CN109824886A - One kind containing DOPO based structures unit poly(aryl ether ketone) CABLE MATERIALS resin and its synthetic method - Google Patents
One kind containing DOPO based structures unit poly(aryl ether ketone) CABLE MATERIALS resin and its synthetic method Download PDFInfo
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- CN109824886A CN109824886A CN201811633402.XA CN201811633402A CN109824886A CN 109824886 A CN109824886 A CN 109824886A CN 201811633402 A CN201811633402 A CN 201811633402A CN 109824886 A CN109824886 A CN 109824886A
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Abstract
The invention discloses one kind to contain DOPO based structures unit poly(aryl ether ketone) CABLE MATERIALS resin and its synthetic method.This method will contain DOPO base bis-phenol, hexafluoro bisphenol-a, difluoro benzophenone and K2CO3Or Na2CO3In molar ratio it is x:(1~x): 1:(1.2~3) it is placed in solvent, in N2Prior to 130~150 DEG C 1~5h of reaction under stream effect, then at 150~170 DEG C of 3~20h of reaction, synthesis contains DOPO based structures unit poly aryl ether ketone polymer.This method is simple and easy to do, and in the polymerization with weak base at salt, synthesis contains DOPO based structures unit poly(aryl ether ketone) CABLE MATERIALS resin.The CABLE MATERIALS made of the above method of the present invention,, high abrasion higher with intensity, high oil resistant, electrical insulating property are good, and there are the characteristics such as low cigarette, Halogen, fire-retardant, electric thin-walled cable is very suitable to squeeze out, 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 poly(aryl ether ketone) containing DOPO based structures unit, and in particular to contains DOPO base containing a kind of
The poly(aryl ether ketone) and its synthetic method of structural unit.
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
Equipment Development is rapid, and 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, height
Dissipation capacity development.The insulating wall thickness of common thin-walled cable is in 0.3mm or more, and high-speed railway and urban track traffic fill
Standby required ultra-thin-wall insulated cable insulation wall thickness requires to be 0.18mm.Currently, cable industry production thin-walled cable is main exhausted
Edge material is cross-linked polyolefin, and due to containing more fire retardant in the CABLE MATERIALS, insulation resistance is smaller, and cable is easy to be hit
It wears, and the physical mechanical property of cable, there are many deficiencies, insulation wall can not achieve ultra-thin, it is difficult to meet the need of manufacturing enterprise
It wants.Therefore, produce high-temperature resistant, high oil resistant, high fire-retardance ultra-thin-wall insulated cable a key technology be exactly research suitably
CABLE MATERIALS.
With the development of technology, domestic also to have extensive research to special cable material, and propose corresponding solution
Scheme.Wherein most important solution concentrate on to traditional material it is composite modified on.For example, CN103275458A is provided
A kind of Polyether-ether-ketocable cable material by the mixing of polyether-ether-ketone, polyester ether, polyphenylene oxide, carbimide etc. improves cable
The performance of material has higher intensity, high abrasion, high oil resistant, electrical insulating property good, and has the characteristics such as low cigarette, Halogen, fire-retardant, fits
Electric thin-walled cable is closed to squeeze out.CN105542390A provides a kind of heat-proof combustion-resistant cable insulating materials, passes through polyether-ether-ketone, chlorine
Fossil waxes, alkyd resin, Lauxite, blanc fixe, asbestos, pentabromoethyl benzene, mica powder, low density polyethylene (LDPE), calcining pottery
The mixing of soil, palm oil, glycerol, aminopropyl trimethoxysilane, bis-phenol, hypo-aluminum orthophosphate, polytetrafluoroethylene (PTFE), modified filler etc..
Fire retardant in the cable material formula of the invention is compounded by borate family fire retardant and phosphor nitrogen combustion inhibitor, adds a small amount of resistance
Combustion synergist just makes CABLE MATERIALS have good flame retardant effect and excellent smoke suppressing effect, and the smoke density of the CABLE MATERIALS is low, toxicity
Index is low.For another example, patent CN105400131A provides a kind of special cable composite material, the special cable composite material
Be made of following component: polyether-ether-ketone, polyethylene, polyimides are mixed in proportion as basis material, using ethylene-acetate
Ethylene copolymer-modified polymer, molybdenum trioxide, magnesia are used as flame-retardant additive after coupling agent treatment, using peroxidating
Diisopropylbenzene (DIPB) is as crosslinking catalyst, using silicon nitride crystal whisker as reinforcing agent, forms composite material by melt blending,
With preferable high temperature resistant property and improved flame retardant effect, the stability that can be realized under bad working environments is not reduced.On
State between polymer formed homogeneous blend it is more difficult, preparation process is required it is complex, and its addition auxiliary agent it is more, undoubtedly
Product cost is increased, the reliability of cable is reduced.Likewise, CN104292601A provides a kind of oil resistant low smoke and zero halogen
Fire-resistant cable material, by the mixing of ethylene-vinyl acetate copolymer, low density polyethylene (LDPE), sulphurated siliastic, polyamide etc.,
Improve the performance of conventional polyolefins blend composition.As it can be seen that overcome many defects in the prior art, need a kind of high temperature resistant,
The special cable of high reliablity fire-retardant, shielding system energy is good substitutes traditional cable material with composite material.
The organic phosphine fire retardant of broad sense is in the majority with phosphate, and mostly liquid, and that there are heat resistances is poor, volatility is big, hair
Smoke is big and polymer compatibility is bad, the surface for being readily migrate into material, the mechanical performance for influencing material is used for a long time etc.
Disadvantage.Reactive flame retardant in the form of polymer monomer, or as crosslinking agent participate in high polymer chemical reaction, after reaction
As a part of Polymer Structure unit, so that material be made to achieve the goal.With simple process, it is wide in variety, have a wide range of application
The advantages that, thermal stability is good, relative mass is big, with material compatibility is good, the high and low cigarette of phosphorus content, nontoxic and with C-P key
Organic phosphine fire retardant.
Poly(aryl 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.It DOPO base bis-phenol structural unit will be contained will be introduced into poly(aryl ether ketone) main chain and prepare
The poly(aryl ether ketone) new varieties of based structures containing DOPO, the resinoid have simultaneously poly(aryl ether ketone) high temperature resistant, corrosion-resistant, radiation hardness and
DOPO fire-retardant advantage.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, provides a kind of easy-to-use containing DOPO based structures list
The poly(aryl ether ketone) and its synthetic method of member.
DOPO base is introduced into poly(aryl ether ketone) side group and synthesizes containing DOPO based structures unit at salt by present invention application weak base
Poly(aryl ether ketone) has intensity height, high abrasion, high oil resistant, electrical insulating property good, and has the characteristics such as low cigarette, Halogen, fire-retardant, very
It is suitble to electricity thin-walled cable to squeeze out, is able to satisfy the processing technology and product technology requirement of ultra-thin-wall insulated cable, convenient for production, tool
There are good economic benefit and promotional value.
The present invention is achieved through the following technical solutions:
One kind containing DOPO based structures unit poly(aryl ether ketone), structure are as follows:
X are as follows: 10~200, y are as follows: 200-x
The invention also discloses a kind of synthetic methods containing DOPO lateral group polyarylether ketone, include the following steps:
It is x:(1~x that DOPO base bis-phenol, bis-phenol, difluoro benzophenone and catalyst will be contained in molar ratio): 1:(1.2~3) it sets
In organic solvent, in N2Prior to 130~150 DEG C 1~5h of reaction under stream effect are closed then at 150~170 DEG C of 3~20h of reaction
At contain DOPO based structures unit ketone-grouped resin.
Wherein, biphenol monomer described in step be hydroquinone, resorcinol, bisphenol fluorene, bisphenol-A, hexafluoro bisphenol-a,
Any one or any two kinds of combination of '-biphenyl diphenol, O-methoxy hydroquinone.
Wherein, the biphenol monomer of base containing DOPO described in step be the hydroquinone containing DOPO, the naphthalenediol containing DOPO or
Double DOPO biphenol methane.
Wherein, the organic solvent is toluene, n,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone
Any one or any two kinds of combination.
Wherein, catalyst 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. being easy to for DOPO base being introduced into poly(aryl ether ketone) side group with the present invention, this method weak base overcomes at salt
Industry is at product caused by salt degradable with NaOH, reacts the problems such as difficult to control and alkali pollution, and obtained high molecular weight contains
DOPO based structures unit poly(aryl ether ketone), containing the equal relative molecular mass of DOPO based structures unit poly(aryl ether ketone) number between 1.5-10
Ten thousand.
2. more stable, bond energy is very strong, very high containing P-C key is contained in DOPO based structures unit poly(aryl ether ketone) structure
At a temperature of can just be broken, in poly(aryl ether ketone) main chain introduce DOPO base bis-phenol structural unit after be still able to maintain its heat-resisting quantity
Can, thus such stability of material is good, flame retardant property is more longlasting.
3. the purpose of the present invention is from Molecular Design, provide in a kind of strand to contain DOPO side group structure
The novel poly(aryl ether ketone) of based structures containing DOPO high-performance polymer, excellent combination property can use the anti-flammability of its DOPO base
Can, 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 is to one made of the invention
A little nonessential modifications and adaptations still fall within protection scope of the present invention.
Embodiment 1
The bis-phenol of base containing DOPO (III) 1.2562g (2mmol), hexafluoro bisphenol-a 6.0521g are sequentially added in three-necked flask
(18mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2Flow down 140
DEG C reaction 3 hours, then heat to 170 DEG C react 10 hours, reaction solution is poured under stiring immediately in deionized water sink
It forms sediment, 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, it will
Sediment is placed in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains product and contains DOPO based structures unit poly(aryl ether ketone).Gpc analysis,
Mn=26200, PDI=2.34.
Embodiment 2.
The bis-phenol of base containing DOPO (II) 1.8817g (5mmol), hexafluoro bisphenol-a 5.0434g are sequentially added in three-necked flask
(15mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2Flow down 140
DEG C reaction 3 hours, then heat to 170 DEG C react 7 hours, reaction solution is poured into deionized water under stiring precipitate immediately,
Filtering.The sediment being obtained by filtration is impregnated with deionized water, it is primary every 3 hours replacement water, it filters, will sink after 24 hours
Starch is placed in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains product and contains DOPO based structures unit poly(aryl ether ketone).Gpc analysis, Mn
=22300, PDI=2.81.
Embodiment 3
The bis-phenol of base containing DOPO (I) 3.2414g (10mmol), hexafluoro bisphenol-a 3.3623g are sequentially added in three-necked flask
(10mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2Flow down 140
DEG C reaction 3 hours, then heat to 170 DEG C react 15 hours, reaction solution is poured under stiring immediately in deionized water sink
It forms sediment, 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, it will
Sediment is placed in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains product and contains DOPO based structures unit poly(aryl ether ketone).Gpc analysis,
Mn=27200, PDI=2.64.
Embodiment 4.
The bis-phenol of base containing DOPO (I) 1.6411g (5mmol), hexafluoro bisphenol-a 3.3623g are sequentially added in three-necked flask
(10mmol), difluoro benzophenone 3.2730g (15mmol), toluene 110mL, DMAc100mL, in 1mL/ seconds N2Flow down 130
DEG C reaction 5 hours, then heat to 150 DEG C react 20 hours, reaction solution is poured under stiring immediately in deionized water sink
It forms sediment, 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, it will
Sediment is placed in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains product and contains DOPO based structures unit poly(aryl ether ketone).Gpc analysis,
Mn=26580, PDI=2.75.
Embodiment 5
The bis-phenol of base containing DOPO (II) 1.5119g (4mmol), '-biphenyl diphenol 2.9794g are sequentially added in three-necked flask
(16mmol), difluoro benzophenone 4.3640g (20mmol), toluene 120mL, N-Methyl pyrrolidone 100mL, at 1mL/ seconds
N2It flows down 150 DEG C to react 4 hours, then heats to 165 DEG C and react 11 hours, immediately pour into reaction solution under stiring
It precipitates, filters in ionized water.The sediment being obtained by filtration is impregnated with deionized water, primary every 3 hours replacement water, 24 is small
When after filter, put the precipitate in 80 DEG C of vacuum drying ovens 10 hours dry, obtain product and contain DOPO based structures unit polyarylether
Ketone.Gpc analysis, Mn=29810, PDI=2.93.
Embodiment 6.
It is sequentially added in three-necked flask containing the bis-phenol of base containing DOPO (II) 1.8817g (5mmol), hexafluoro bisphenol-a
3.3623g (10mmol), difluoro benzophenone 3.2730g (15mmol), toluene 120mL, DMAc100mL, in 1mL/ seconds N2
It flows down 135 DEG C to react 3 hours, then heats to 170 DEG C and react 5 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 product and contain DOPO based structures unit poly(aryl ether ketone).GPC
Analysis, Mn=25810, PDI=2.53.
Embodiment 7
The bis-phenol of base containing DOPO (III) 6.2800g (10mmol), resorcinol 1.1101g are sequentially added in three-necked flask
(10mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2Flow down 140
DEG C reaction 3 hours, then heat to 170 DEG C react 10 hours, reaction solution is poured under stiring immediately in deionized water sink
It forms sediment, 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, it will
Sediment is placed in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains product and contains DOPO based structures unit poly(aryl ether ketone).Gpc analysis,
Mn=25345, PDI=2.89.
Embodiment 8
The bis-phenol of base containing DOPO (III) 2.5128g (4mmol), hydroquinone 1.7616g are sequentially added in three-necked flask
(16mmol), difluoro benzophenone 4.3640g (20mmol), toluene 80mL, DMAc100mL, in 1mL/ seconds N2Flow down 140
DEG C reaction 3 hours, then heat to 170 DEG C react 20 hours, reaction solution is poured under stiring immediately in deionized water sink
It forms sediment, 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, it will
Sediment is placed in drying 10 hours in 80 DEG C of vacuum drying ovens, obtains product and contains DOPO based structures unit poly(aryl ether ketone).Gpc analysis,
Mn=25345, PDI=2.89.
Claims (7)
1. one kind contains DOPO based structures unit poly(aryl ether ketone) CABLE MATERIALS resin, it is characterised in that the resin has following DOPO
Biphenol monomer (I), (II) or (III):
2. one kind contains DOPO based structures unit poly(aryl ether ketone) CABLE MATERIALS resin, it is characterised in that the resin has following chemistry
Structural formula:
X are as follows: 10~200, y are as follows: 200-x.
3. a kind of synthetic method containing DOPO based structures unit poly(aryl ether ketone) CABLE MATERIALS resin, it is characterised in that the synthesis side
Method includes the following steps: that will contain DOPO base bis-phenol, bis-phenol, difluoro benzophenone and catalyst is x:(1~x in molar ratio): 1:
(1.2~3) are placed in solvent, in N2Stream effect under prior to 130~150 DEG C 1~5h of reaction, then at 150~170 DEG C react 3~
20h synthesizes linear DOPO based structures unit poly(aryl ether ketone).
4. a kind of synthetic method containing DOPO based structures unit ketone-grouped resin according to claim 3, feature
Be: the dihydric phenol monomer of base containing DOPO in the step is the hydroquinone containing DOPO, the naphthalenediol containing DOPO or double DOPO
Biphenol methane.
5. a kind of synthetic method containing DOPO based structures unit ketone-grouped resin according to claim 3, feature
Be the solvent be one or both of toluene, n,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone and
Combination of the above object.
6. a kind of synthetic method containing DOPO based structures unit ketone-grouped resin according to claim 3, feature
It is that the bis-phenol is hexafluoro bisphenol-a, bisphenol-A, adjacent methyl hydroquinone, hydroquinone, resorcinol, '-biphenyl diphenol or bis-phenol
The composition of one or both of fluorenes or more.
7. the synthetic method according to claim 3 containing DOPO based structures unit poly(aryl ether ketone), it is characterised in that described
Catalyst is Anhydrous potassium carbonate or natrium carbonicum calcinatum.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565503A (en) * | 2009-05-27 | 2009-10-28 | 深圳大学 | Polyarylether with phosphaphenanthrene structure and method for synthesizing the same |
| CN106947075A (en) * | 2017-03-24 | 2017-07-14 | 福州通尔达电线电缆有限公司 | A kind of PAEK CABLE MATERIALS resin and its synthetic method |
-
2018
- 2018-12-29 CN CN201811633402.XA patent/CN109824886A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565503A (en) * | 2009-05-27 | 2009-10-28 | 深圳大学 | Polyarylether with phosphaphenanthrene structure and method for synthesizing the same |
| CN106947075A (en) * | 2017-03-24 | 2017-07-14 | 福州通尔达电线电缆有限公司 | A kind of PAEK CABLE MATERIALS resin and its synthetic method |
Non-Patent Citations (3)
| Title |
|---|
| THORSTEN HOFFMANN ET AL.: ""Novel phosphorous-containing aromatic polyethers - synthesis and characterization"", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
| XUEXIA XIE ET AL.: ""Novel phosphorous-nitrogen containing poly(aryl ether ketone)s: synthesis, characterization, and thermal properties"", 《DESIGNED MONOMERS AND POLYMERS》 * |
| 唐旭东等: ""新型含磷双酚A型共聚醚醚酮的合成与性能"", 《应用化学》 * |
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