CN108341947A - The intrinsic fire-retardant semi-aromatic of one kind being total to polyarylether amide and preparation method thereof - Google Patents
The intrinsic fire-retardant semi-aromatic of one kind being total to polyarylether amide and preparation method thereof Download PDFInfo
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- CN108341947A CN108341947A CN201810131931.3A CN201810131931A CN108341947A CN 108341947 A CN108341947 A CN 108341947A CN 201810131931 A CN201810131931 A CN 201810131931A CN 108341947 A CN108341947 A CN 108341947A
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- 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
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
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- 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
- C08G65/4093—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 characterised by the process or apparatus used
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Abstract
The invention discloses a kind of intrinsic fire-retardant semi-aromatics to be total to polyarylether amide and preparation method thereof, utilize phosphorous/silicon diphenol monomer or siliceous difluoro diamides or phosphorous difluoro diamides monomer, pass through solution polycondensation, it is prepared for fire-retardant half aromatic co aryl oxide amide, the intrinsic viscosity [η] of the half aromatic co aryl oxide amide is 0.65 1.01 dL/g, 0 grade of 2 V of vertical combustion grade V, limit oxygen index are 26.8 45.5%, and tensile strength is 65 108 MPa.Intrinsic fire-retardant half aromatic co aryl oxide amide disclosed in this invention has the characteristics that halogen-free flameproof, not molten drop, easy processing, high mechanical properties, it is made to have widely application as engineering plastics.
Description
Technical field
The invention belongs to synthesize flame retarded polymeric material technical field.Specifically, the present invention relates to one kind to contain phosphorus, silicon
Total polyarylether amide of element and preparation method thereof.
Background technology
Semiaromatic polyamide composition has excellent mechanical property and chemical-resistant, and ten are applied in daily life
Divide extensively, especially in industries such as electronic apparatus, automobile making and aerospaces.However the process window of semiaromatic polyamide composition compared with
It is narrow, and with combustibility, make its application being restricted to a certain extent.
Semi-aromatic polyarylether amide is as a kind of high performance plastics, not only with polyarylether and semiaromatic polyamide composition
Excellent mechanical property, thermal property, and the toughness and processing fluidity of polyarylether are improved, while improving semi-aromatic
The narrow defect of polyamide process window.In addition, semi-aromatic polyarylether amide have high income, molecular weight height, easy processing,
High temperature resistant, it is corrosion-resistant the advantages that (103739839 A of CN).However, semi-aromatic polyarylether amide has combustibility, it is made to answer
With being restricted to a certain extent.And also have relevant report in recent years for the flame-retardant modified research of polyamide, but it is big
Majority is to realize that its is fire-retardant by adding fire retardant.Such as (CN201380045938.9) halogen-free flame-retardant polyamides of E.I.Du Pont Company
Amine, it was recently reported that addition halogen-free flame retardants realizes the fire-retardant of polyamide, and this method adds there are additive and substrate compatibility are poor
Add agent that can migrate, the problems such as fire-retardant persistence is poor.
Invention content
The purpose of the present invention is provide a kind of intrinsic fire-retardant half aromatic co aryl oxide amide in view of the deficiencies of the prior art
And preparation method thereof, its main feature is that flame-retardant monomer and aromatic series diphenol, semi-aromatic difluoro diamides are copolymerized, prepare half
Aromatic co aryl oxide amide also has the advantages that high temperature resistant, good mechanical property while making it have excellent flame retardant property,
To there is wider application.
The intrinsic fire-retardant half aromatic co aryl oxide amide of the offer of the present invention, the host molecule general structure of the polymer
For：
Wherein：M, n are mole percent, m+n=100；
In any one.
Further, when in formula one n be 5-30mol%, i.e. Ar2Molar content be 2.5-15mol%, be prepared into
The semi-aromatic arrived be total to polyarylether amide intrinsic viscosity [η] be 0.69-1.01dL/g, limit oxygen index 30.0-45.5%,
UL-94 vertical combustion grades are V-2-V-0 grades, tensile strength 68-108MPa；
When n is 5-30mol%, i.e. R in formula two2Molar content be 2.5-15mol%, the semiaromatic being prepared
The intrinsic viscosity [η] that race is total to polyarylether amide is 0.65-0.98dL/g, and limit oxygen index 26.8-38.5%, UL-94 is vertical
Combustion rating is stepless V-2-V-0 grades, tensile strength 65-105MPa.
Further, the structure Ar1Any one in following diphenol：
Structure Ar2Any one in following diphenol：
Any one of structure R1 in following semi-aromatic difluoro diamides：
Any one of structure R2 in following difluoro diamides：
The method provided by the invention for preparing intrinsic fire-retardant half aromatic co aryl oxide amide is specially：
(1) when preparing the intrinsic fire-retardant half aromatic co aryl oxide amide as described in formula one, include the following steps：
In the reaction vessel, Ar is obtained described in being added1Diphenol DHTPM or any one of FDP or PEBP, described
Obtain Ar2Diphenol DOPO-HQ or any one of 2DOPO-DMSi or 2DOPO-DPSi, described obtain R1Semi-aromatic
Difluoro diamides BFBB or BFBH or any one of BFBO or BFBD, catalyst, dehydrating agent, high boiling solvent, in indifferent gas
It under body protection, heats up and certain temperature is kept to be reacted, obtain, containing the solution of the copolymer as described in formula one, being purified
Afterwards, the intrinsic fire-retardant half aromatic co aryl oxide amide as described in formula one is obtained；
(2) when preparing the intrinsic fire-retardant half aromatic co aryl oxide amide as described in formula two, include the following steps：
In the reaction vessel, Ar is obtained described in being added1Diphenol DHTPM or any one of FDP or PEBP, described
Obtain R2Any one of difluoro diamides BFBPSi or BFPPO, described obtain R1Semi-aromatic difluoro diamides BFBB
Or BFBH or any one of BFBO or BFBD, catalyst, dehydrating agent, high boiling solvent heat up simultaneously under inert gas protection
It keeps certain temperature to be reacted, obtains, containing the liquid of the copolymer as described in formula two, after being purified, obtaining as described in formula two
Intrinsic fire-retardant half aromatic co aryl oxide amide.
Further, the reaction condition in above-mentioned reaction is：Temperature is controlled in 150-190 DEG C of dehydration 1-6h, in temperature
190-220 DEG C of the reaction was continued 6-12h of degree.
Further, what is be added in preparation method described obtains Ar2Any diphenol account for moles the hundred of overall reaction raw material
Point content is 2.5-15mol%, and the described of addition obtains R2Any difluoro diamides account for moles the hundred of overall reaction raw material
It is 2.5-15mol% to divide content.
Further, the catalyst described in preparation method is one kind in sodium carbonate, potassium carbonate, cesium carbonate；Described
Dehydrating agent is one kind in toluene, ethylbenzene, ortho-xylene, meta-xylene, paraxylene；The inert gas is nitrogen, argon
One kind in gas；High boiling solvent is one kind in formamide, acetamide, N-Methyl pyrrolidone, sulfolane.
Further, the purification step described in preparation method is specially：Above-mentioned reacting liquid temperature is controlled in 80-150
DEG C, then reaction solution is poured into deionized water, filamentous polymer is precipitated, is then washed with water, ethyl alcohol, is then dried repeatedly
Drying recycles pulverizer to crush polymer, is washed again with water, ethyl alcohol, is dried in vacuo, and semi-aromatic is made and is copolymerized aryl oxide acyl
Amine.
Further, Ar is obtained described in preparation method2Phosphorous/silicon diphenol 2DOPO-DMSi or 2DOPO-DPSi it is logical
Following steps are crossed to be prepared：In the reaction vessel, by 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrenes -
10- oxides (DOPO-HQ), are dissolved in organic solvent, keep that dichlorosilane solution is added dropwise when certain temperature；It also needs to be added
Acid binding agent, acid binding agent can be triethylamine；After dichlorosilane is added dropwise, holding is reacted at a certain temperature, and generation contains
The reaction solution for having the phosphorous/silicon diphenol after being purified, obtains the phosphorous/silicon diphenol；
Further, in above-mentioned preparation method, dichlorosilane solution is added dropwise when temperature is controlled at 5-25 DEG C, dripping quantity is
DOPO-HQ：Dichlorosilane=2-2.5；Triethylamine can be dissolved in before dichlorosilane solution is added dropwise in organic solvent, also may be used
To be added after dropping, or it is added dropwise together with dichlorosilane solution；After dichlorosilane is added dropwise, temperature is controlled in 25-
60 DEG C, react 10-24h.
Selected organic solvent is at least one of formamide, dimethylformamide, dimethylacetylamide.
Purification step described in preparation method is specially：By above-mentioned reaction solution ethyl alcohol low-temperature precipitation, then again with weight
Recrystallisation solvent recrystallizes, and phosphorus/silicon diphenol is made in vacuum drying.
Recrystallization solvent is at least one of methanol, ethyl alcohol, isopropanol, tetrahydrofuran.
Further, siliceous or phosphorous difluoro the diamides BFBPSi or BFPPO for obtaining R2 described in preparation method are logical
Following steps are crossed to be prepared：By siliceous diamines or phosphorous diamines, triethylamine is as acid binding agent, and room-temperature dissolution is in dichloromethane
In；In the reaction vessel, dichloromethane is added, fluorobenzoyl chloride will be then dissolved in dichloromethane, and be then added above-mentioned
The siliceous diamines configured or phosphorous diamine solution, after diamine solution drips, the reaction was continued at room temperature a period of time,
The reaction solution containing the siliceous or phosphorous difluoro diamides is generated, after being purified, obtains described siliceous or phosphorous two
Fluorine diamides.
Further, in above-mentioned preparation method, after diamine solution drips, the reaction was continued at room temperature, and the time is 8h.
Purification step described in preparation method is specially：Above-mentioned reaction solution is filtered, triethylamine hydrochloride is removed, is collected
Filtrate then rotates, and removes solvent, collects solid, is washed with deionized, and ethyl alcohol recrystallization, vacuum drying is then used to obtain
Siliceous or phosphorous difluoro diamides.
The present invention has the following advantages：
1, the synthesis of flame-retardant monomer provided by the invention have preparation process is simple, reaction condition is mild, product yield is high,
Pollute the advantages that small and solvent is easy recycling.
2, the present invention is copolymerized using " one kettle way " solution polycondensation, is prepared for intrinsic fire-retardant semi-aromatic copolymerization aryl oxide acyl
Amine, the polymer have synthesis simply, and are halogen-free flameproof, belong to environment-friendly material.
3, flame-retardant monomer is introduced polymer by the present invention, need to only introduce the flame-retardant monomer of minor proportion (≤15mol%), partly
Aromatic copolyester aryl oxide amide can reach fire-retardant well and anti-dropping effect, this is mainly the introducing of siliceous flame-retardant monomer,
So that material is easier into charcoal and enhances the stability of layer of charcoal in burning, condensed phase fire retardation, at the same time, phosphorus are realized
The introducing of element is combined with element silicon, has synergistic fire retardation.
4, intrinsic fire-retardant half aromatic co aryl oxide amide provided by the invention has excellent anti-flammability, easy processing, resistance to height
The advantages that warm, while the mechanical property for keeping polymer excellent, this is mainly the presence of phenyl ring side group in copolymer, to polymerize
There are π-πconjugations between object strand so that the mechanical property of material is kept well.
5, intrinsic fire-retardant half aromatic co aryl oxide amide provided by the invention cannot be only used for preparing heat-resisting, resistant to chemical etching
Component and product, may be made as special fibre and film, can also be blended to use, be allowed to other macromolecule polyalcohols
It can also assign material the fire-retardant characteristic with anti-dropping while improving material mechanical performance, thus, it has a wide range of applications
Foreground.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of BFBPSi prepared by the embodiment of the present invention 37, it can be seen from the figure that 0.1ppm
For the hydrogen chemical shifts of methyl on siloxanes, 1.3ppm, 1.6ppm, 3.2ppm are respectively the chemical potential of the hydrogen of three methylene
It moves, 6.8ppm is the chemical shift of hydrogen on amide, 7.0ppm and the chemical shift that 7.7ppm is hydrogen on phenyl ring, illustrates siliceous difluoro
Diamides BFBPSi is successfully synthesized.
Fig. 2 is the nuclear magnetic resonance spectroscopy that bisphenol fluorene containing BFBPSi prepared by the embodiment of the present invention 43 is copolymerized aryl oxide adipamide
Figure illustrates successfully it can be seen from the figure that 0.1ppm is the hydrogen chemical shifts of methyl on siloxanes by flame-retardant monomer BFBPSi
It is introduced into copolymer.
Fig. 3 is that the UL-94 of the copolymerization aryl oxide adipamide of bisphenol fluorene containing BFBPSi prepared by the embodiment of the present invention 43 vertically fires
Burn the digital photograph figure of sample after test and limit oxygen index test, it can be seen from the figure that the copolymer have it is certain at
Carbon flame-proof acts on.
The tensile strength curve for the copolymer that Fig. 4 is comparative example 2 of the present invention, prepared by embodiment 42, embodiment 43, from figure
It can be seen that copolymer has good mechanical performance.
Specific implementation mode
Embodiment is given below so that the invention will be further described.It is necessarily pointed out that following embodiment cannot
Be interpreted as limiting the scope of the invention, if the person skilled in the art in the field according to aforementioned present invention content to this hair
It is bright to make some nonessential modifications and adaptations, still fall within the scope of the present invention.
In addition, it is worth noting that：1) characteristic of the intrinsic fire-retardant half aromatic co aryl oxide amide obtained by following embodiment
Glutinous number [η] is to be configured to the solution of a concentration of 0.5g/dL for solvent with N-methyl pyrrolidones (NMP), use dark type viscometer
It is tested at 25 DEG C；2) limit oxygen index of test product is to be made into 120 × 6.5 × 3.2mm3Standard oxygen index (OI) sample
Item is measured according to ASTM D2863-97 standards on HC-2 oxygen index instruments；3) vertical combustion be then be made into 120 ×
13.0×3.2mm3Standard batten measured using CZF-2 type Vertical combustion instruments according to UL-94 standards；4) U.S.'s English is used
3366 type universal material tester for elongation of Si Telang Instron presses GB/T 1040.2-2006 (ISO 527-2:1993) standard
The test of tensile property is carried out to sample.
Embodiment 1
By (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (212g, 2mol) sodium carbonate, 200ml toluene,
(332.5g, 0.95mol) 9,9- bis- (4- hydroxy phenyls) fluorenes (also known as bisphenol fluorene, FDP), (16.2g, 0.05mol) DOPO-HQ and
Reaction vessel is added in 1500ml formamides, then under nitrogen protection, in 175 DEG C of dehydration 3h of temperature, then in 200 DEG C of temperature
8h is reacted, sticky copolymer solution is obtained；Copolymer solution is purified later, the specific steps are：Above-mentioned solution is cold
But it to 120 DEG C, is poured into water while stirring, grey fine strip shape polymer crude product is precipitated；Above-mentioned polymer is washed through water, ethyl alcohol
It washs, in 80 DEG C of dry 8h, crushes, then washed respectively with deionized water, ethyl alcohol, in 80 DEG C of dry l0h of temperature to get to after purification
Bisphenol fluorene containing DOPO-HQ is copolymerized aryl oxide succinamide.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.83dL/g；Limit oxygen index is 31.5%；Vertical combustion
Grade is V-1, tensile strength 85MPa.
Embodiment 2~4
Raw material proportioning adjustment in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 1, is prepared difference
The bisphenol fluorene of DOPO-HQ contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 1.
Table 1
Embodiment 5
By (360g, 1mol) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH), (276g, 2mol) potassium carbonate, 200ml is to diformazan
Benzene, (334.5g, 0.95mol) 4,4'- diphenyl methylenes bis-phenol (also known as bisphenol b P, DHTPM), (16.2g, 0.05mol) DOPO-
Reaction vessel is added in HQ and 1500ml sulfolane, then under nitrogen protection, in 190 DEG C of dehydration 1h of temperature, then in temperature
200 DEG C of reaction 12h, obtain sticky copolymer solution, above-mentioned solution are cooled to 80 DEG C, is poured into water while stirring, be precipitated
Grey fine strip shape polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then spend respectively
Ionized water, ethyl alcohol washing are copolymerized aryl oxide adipyl in 80 DEG C of dry l0h of temperature to get to the bisphenol b P after purification containing DOPO-HQ
Amine.
The intrinsic viscosity [η] of the copolymerization aryl oxide adipamide is 0.82dL/g；Limit oxygen index is 30.5%；Vertical combustion
Grade is V-2, tensile strength 82MPa.
Embodiment 6~8
Raw material proportioning adjustment in bisphenol b P copolymerization aryl oxide adipamides prepared by embodiment 5, is prepared difference
The bisphenol b P of DOPO-HQ contents is copolymerized aryl oxide adipamide, and specific data are shown in Table 2.
Table 2
Embodiment 9
By (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene,
(275.5g, 0.95mol) 4,4'- (1- phenethyls) bis-phenol (also known as bisphenol-ap, PEBP), (16.2g, 0.05mol) DOPO-HQ and
Reaction vessel is added in 1500ml sulfolane, then under nitrogen protection, in 150 DEG C of dehydration 6h of temperature, then in 220 DEG C of temperature
6h is reacted, sticky copolymer solution is obtained, above-mentioned solution is cooled to 120 DEG C, is poured into water while stirring, it is thin that grey is precipitated
Strip polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use deionization respectively
Water, ethyl alcohol washing, aryl oxide succinamide is copolymerized in 80 DEG C of dry l0h of temperature to get to the bisphenol-ap after purification containing DOPO-HQ.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.85dL/g；Limit oxygen index is 30.0%；Vertical combustion
Grade is V-1, tensile strength 95MPa.
Embodiment 10~12
Raw material proportioning adjustment in bisphenol-ap copolymerization aryl oxide succinamide prepared by embodiment 9, is prepared difference
The bisphenol-ap of DOPO-HQ contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 3.
Table 3
Embodiment 13
(1) preparation of 2DOPO-DMSi：By (356.4g, 1.1mol) 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxygen
Reaction is added in miscellaneous -10- phospho hetero phenanthrenes -10- oxides (DOPO-HQ), (101g, 1mol) triethylamine, 2000ml dimethylacetylamides
Container, nitrogen protection, temperature control is at 5 DEG C, mechanical agitation.Then, it is added dropwise and prepares solution [(64.5g, 0.5mol) dichloro diformazan
Base silane, 500ml dimethylacetylamides], 1 drop is per second；After being added dropwise, temperature is controlled at 40 DEG C, and reaction for 24 hours, is clarified
Transparency liquid；By above-mentioned reaction solution ethyl alcohol low-temperature precipitation, ethyl alcohol weight crystal, 2DOPO-DMSi is made in vacuum drying.
(2) by (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (212g, 2mol) sodium carbonate, 200ml first
Benzene, (332.5g, 0.95mol) 9,9- bis- (4- hydroxy phenyls) fluorenes (also known as bisphenol fluorene, FDP), (35.2g, 0.05mol) 2DOPO-
Reaction vessel is added in DMSi and 1500ml N-methyl pyrrolidones, then under nitrogen protection, in 170 DEG C of dehydrations of temperature
3h, then in 200 DEG C of reaction 8h of temperature, obtain sticky copolymer solution, above-mentioned solution is cooled to 150 DEG C, is fallen while stirring
Enter in water, grey fine strip shape polymer crude product is precipitated；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, powder
It is broken, then washed respectively with deionized water, ethyl alcohol, in 80 DEG C of dry l0h of temperature to get to the bis-phenol after purification containing 2DOPO-DMSi
Fluorenes is copolymerized aryl oxide succinamide.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.82dL/g；Limit oxygen index is 33.5%；Vertical combustion
Grade is V-1, tensile strength 88MPa.
Embodiment 14~16
Raw material proportioning adjustment in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 13, is prepared difference
The bisphenol fluorene of 2DOPO-DMSi contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 4.
Table 4
Embodiment 17
By (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (212g, 2mol) sodium carbonate, 200ml ethylbenzene,
(334.5g, 0.95mol) 4,4'- diphenyl methylenes bis-phenol (also known as bisphenol b P, DHTPM), (35.2g, 0.05mol) 2DOPO-
Reaction vessel is added in DMSi and 1500ml sulfolane, then under nitrogen protection, in 170 DEG C of dehydration 4h of temperature, then in temperature
220 DEG C of reaction 6h of degree, obtain sticky copolymer solution, above-mentioned solution are cooled to 120 DEG C, is poured into water while stirring, analyse
Go out grey fine strip shape polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use respectively
Deionized water, ethyl alcohol washing are copolymerized aryl oxide in 100 DEG C of dry l0h of temperature to get to the bisphenol b P after purification containing 2DOPO-DMSi
Succinamide.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.85dL/g；Limit oxygen index is 32.3%；Vertical combustion
Grade is V-2, tensile strength 79MPa.
Embodiment 18~20
Raw material proportioning adjustment in bisphenol b P copolymerization aryl oxide succinamides prepared by embodiment 17, is prepared difference
The bisphenol b P of 2DOPO-DMSi contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 5.
Table 5
Embodiment 21
By (360g, 1mol) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH), (276g, 2mol) potassium carbonate, 200ml toluene,
(203.0g, 0.70mol) 4,4'- (1- phenethyls) bis-phenol (also known as bisphenol-ap, PEBP), (35.2g, 0.05mol) 2DOPO-
Reaction vessel is added in DMSi and 1500ml sulfolane, then under nitrogen protection, in 160 DEG C of dehydration 4h of temperature, then in temperature
190 DEG C of reaction 12h of degree, obtain sticky copolymer solution, above-mentioned solution are cooled to 120 DEG C, is poured into water while stirring, analyse
Go out grey fine strip shape polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use respectively
Deionized water, ethyl alcohol washing, aryl oxide is copolymerized in 80 DEG C of dry l0h of temperature to get to the bisphenol-ap after purification containing 2DOPO-DMSi
Adipamide.
The intrinsic viscosity [η] of the copolymerization aryl oxide adipamide is 0.85dL/g；Limit oxygen index is 31.2%；Vertical combustion
Grade is V-1, tensile strength 105MPa.
Embodiment 22~24
Raw material proportioning adjustment in bisphenol-ap copolymerization aryl oxide adipamide prepared by embodiment 21, is prepared difference
The bisphenol-ap of 2DOPO-DMSi contents is copolymerized aryl oxide adipamide, and specific data are shown in Table 6.
Table 6
Embodiment 25
(1) preparation of 2DOPO-DPSi：By (356.4g, 1.1mol) 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxygen
Reaction is added in miscellaneous -10- phospho hetero phenanthrenes -10- oxides (DOPO-HQ), (101g, 1mol) triethylamine, 2000ml dimethylacetylamides
Container, nitrogen protection, temperature control is at 10 DEG C or so, mechanical agitation.Then, it is added dropwise and prepares solution [(126.5g, 0.5mol) two
Diphenyl dichlorosilane, 500ml dimethylacetylamides], 1 drop is per second；After being added dropwise, temperature is controlled at 60 DEG C, is reacted 12h, is obtained
To clear liquid；By above-mentioned reaction solution ethyl alcohol low-temperature precipitation, recrystallizing methanol, 2DOPO-DPSi is made in vacuum drying.
(2) by (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (652g, 2mol) cesium carbonate, 200ml neighbours
Dimethylbenzene, (332.5g, 0.95mol) 9,9- bis- (4- hydroxy phenyls) fluorenes (also known as bisphenol fluorene, FDP), (41.4g, 0.05mol)
Reaction vessel is added in 2DOPO-DPSi and 1500ml N-methyl pyrrolidones, then under nitrogen protection, in 185 DEG C of dehydrations of temperature
2.5h is reacted, then in 200 DEG C of reaction 8h of temperature, obtains sticky copolymer solution, above-mentioned solution is cooled to 150 DEG C, while stirring
It mixes side to be poured into water, grey fine strip shape polymer crude product is precipitated；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dryings
8h is crushed, then is washed respectively with deionized water, ethyl alcohol, in 100 DEG C of dry l0h of temperature to get to after purification containing 2DOPO-DPSi
Bisphenol fluorene be copolymerized aryl oxide succinamide.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.80dL/g；Limit oxygen index is 35.5%；Vertical combustion
Grade is V-0, tensile strength 88MPa.
Embodiment 26~28
Raw material proportioning adjustment in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 25, is prepared difference
The bisphenol fluorene of 2DOPO-DPSi contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 7.
Table 7
Embodiment 29~32
(332g, 1mol) bis- (4- fluorobenzoyls) fourths in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 25
Diamines (BFBB) replaces with (416g, 1mol) bis- (4- fluorobenzoyls) decamethylene diamines (BFBD), and the adjustment of other raw material proportionings is shown in Table 8,
The bisphenol fluorene copolymerization aryl oxide decanediamide of different 2DOPO-DPSi contents is prepared.
Table 8
Embodiment 33
By (360g, 1mol) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH), (652g, 2mol) cesium carbonate, 200ml toluene,
(275.5g, 0.95mol) 4,4'- (1- phenethyls) bis-phenol (also known as bisphenol-ap, PEBP), (41.4g, 0.05mol) 2DOPO-
Reaction vessel is added in DPSi and 1500ml acetamides, then under nitrogen protection, in 170 DEG C of dehydration 3h of temperature, then in temperature
200 DEG C of reaction 8h of degree, obtain sticky copolymer solution, above-mentioned solution are cooled to 120 DEG C, is poured into water while stirring, analyse
Go out grey fine strip shape polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use respectively
Deionized water, ethyl alcohol washing, aryl oxide is copolymerized in 80 DEG C of dry l0h of temperature to get to the bisphenol-ap after purification containing 2DOPO-DPSi
Adipamide.
The intrinsic viscosity [η] of the copolymerization aryl oxide adipamide is 1.01dL/g；Limit oxygen index is 31.6%；Vertical combustion
Grade is V-1, tensile strength 108MPa.
Embodiment 34~36
Raw material proportioning adjustment in bisphenol-ap copolymerization aryl oxide adipamide prepared by embodiment 33, is prepared difference
The bisphenol-ap of 2DOPO-DPSi contents is copolymerized aryl oxide adipamide, and specific data are shown in Table 9.
Table 9
Embodiment 37
(1) preparation of BFBPSi：By (248.5g, 1mol) 1,3- bis- (3- aminopropyls) -1,1,3,3- tetramethyl, two silicon
Oxygen alkane, (212.5g, 2.1mol) triethylamine, be added 750ml dichloromethane in it is evenly dispersed, be configured to solution；To again (333g,
2.1mol) to fluorobenzoyl chloride, 2000ml dichloromethane is added reaction vessel, and temperature control is at 5 DEG C or so, mechanical agitation, nitrogen
Gas shielded.Then, above-mentioned preparation solution is added dropwise；After being added dropwise, temperature is controlled at 15 DEG C, stops reaction after reacting 8h；It will be upper
It states reaction system to filter, removes triethylamine hydrochloride, collect filtrate, revolving removes dichloromethane, and after washing 3 times, ethyl alcohol carries out
Recrystallization, precipitates crystal, and is dried in vacuo, and BFBPSi is made.
(2) by (315.4g, 0.95mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (24.6g, 0.05mol)
BFBPSi, (276g, 2mol) potassium carbonate, 200ml meta-xylenes, (350g, 1mol) 9,9- bis- (4- hydroxy phenyls) fluorenes are (also known as double
Phenol fluorenes, FDP) and 1500ml acetamides addition reaction vessel, then under protection of argon gas, in 185 DEG C of dehydration 2h of temperature, then
In 200 DEG C of reaction 8h of temperature, sticky copolymer solution is obtained, above-mentioned solution is cooled to 120 DEG C, pours into water while stirring
In, grey fine strip shape polymer crude product is precipitated；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then
It is washed respectively with deionized water, ethyl alcohol, virtue is copolymerized to get to the bisphenol fluorene after purification containing BFBPSi in 100 DEG C of dry l0h of temperature
Ether succinamide.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.85dL/g；Limit oxygen index is 31.5%；Vertical combustion
Grade is V-1, tensile strength 88MPa.
Embodiment 38~40
Raw material proportioning adjustment in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 37, is prepared difference
The bisphenol fluorene of BFBPSi contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 10.
Table 10
Embodiment 41~44
Bis- (4- fluorobenzoyls) butanediamine of raw material in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 37
(BFBB) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH) are replaced with, the adjustment of other raw material proportionings is shown in Table 11, difference is prepared
The bisphenol fluorene of BFBPSi contents is copolymerized aryl oxide adipamide.
Table 11
Embodiment 45~48
Bis- (4- fluorobenzoyls) butanediamine of raw material in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 37
(BFBB) bis- (4- fluorobenzoyls) octamethylenediamines (BFBO) are replaced with, the adjustment of other raw material proportionings is shown in Table 12, difference is prepared
The bisphenol fluorene of BFBPSi contents is copolymerized aryl oxide suberamide.
Table 12
Embodiment 49
By (315.4g, 0.95mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (24.6g, 0.05mol) BFBPSi,
(276g, 2mol) potassium carbonate, 200ml toluene, (352g, 1mol) 4,4'- diphenyl methylenes bis-phenol (also known as bisphenol b P, DHTPM)
Reaction vessel is added with 1500ml acetamides, then under protection of argon gas, in 190 DEG C of dehydration 2h of temperature, then in temperature 200
DEG C reaction 8h, obtain sticky copolymer solution, above-mentioned solution be cooled to 120 DEG C, is poured into water while stirring, be precipitated grey
Fine strip shape polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use deionization respectively
Water, ethyl alcohol washing are copolymerized aryl oxide succinamide in 100 DEG C of dry l0h of temperature to get to the bisphenol b P after purification containing BFBPSi.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.78dL/g；Limit oxygen index is 29.5%；Vertical combustion
Grade is V-2, tensile strength 80MPa.
Embodiment 50~52
Raw material proportioning adjustment in bisphenol b P copolymerization aryl oxide succinamides prepared by embodiment 49, is prepared difference
The bisphenol b P of BFBPSi contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 13.
Table 13
Embodiment 53
By (315.4g, 0.95mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (24.6g, 0.05mol) BFBPSi,
(276g, 2mol) potassium carbonate, 200ml toluene, (290g, 1mol) 4,4'- (1- phenethyls) bis-phenol (also known as bisphenol-ap, PEBP) and
Reaction vessel is added in 1500ml acetamides, then under protection of argon gas, in 170 DEG C of dehydration 3h of temperature, then in 200 DEG C of temperature
8h is reacted, sticky copolymer solution is obtained, above-mentioned solution is cooled to 120 DEG C, is poured into water while stirring, it is thin that white is precipitated
Strip polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use deionization respectively
Water, ethyl alcohol washing, aryl oxide succinamide is copolymerized in 100 DEG C of dry l0h of temperature to get to the bisphenol-ap after purification containing BFBPSi.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.83dL/g；Limit oxygen index is 28.0%；Vertical combustion
Grade is V-2, tensile strength 94MPa.
Embodiment 54~56
Raw material proportioning adjustment in bisphenol-ap copolymerization aryl oxide succinamide prepared by embodiment 53, is prepared difference
The bisphenol-ap of BFBPSi contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 14.
Table 14
Embodiment 57
(1) preparation of BFPPO：By (308g, 1mol) bis- (3- aminophenyls) phenyl phosphine oxides, (212.5g, 2.1mol)
Triethylamine, be added 750ml dichloromethane in it is evenly dispersed, be configured to solution；Again by (333g, 2.1mol) to fluorobenzoyl chloride,
Reaction vessel is added in 2000ml dichloromethane, and temperature control is at 5 DEG C or so, mechanical agitation, nitrogen protection.Then, it is added dropwise above-mentioned
Prepare solution；After being added dropwise, temperature is controlled at 15 DEG C, stops reaction after reacting 8h；Above-mentioned reaction system is filtered, removes three
Ethylamine hydrochloride collects filtrate, and revolving removes dichloromethane, and after washing 3 times, ethyl alcohol is recrystallized, and is precipitated crystal, vacuum
It is dry, BFPPO is made.
(2) by (315.4g, 0.95mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (27.6g, 0.05mol) BFPPO,
(276g, 2mol) potassium carbonate, 200ml toluene, (350g, 1mol) 9,9- bis- (4- hydroxy phenyls) fluorenes (also known as bisphenol fluorene, FDP) and
Reaction vessel is added in 1500ml formamides, then under nitrogen protection, in 185 DEG C of dehydration 2h of temperature, then in 200 DEG C of temperature
8h is reacted, sticky copolymer solution is obtained, above-mentioned solution is cooled to 120 DEG C, is poured into water while stirring, it is thin that grey is precipitated
Strip polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use deionization respectively
Water, ethyl alcohol washing, aryl oxide succinamide is copolymerized in 100 DEG C of dry l0h of temperature to get to the bisphenol fluorene after purification containing BFPPO.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.80dL/g；Limit oxygen index is 30.5%；Vertical combustion
Grade is V-1, tensile strength 88MPa.
Embodiment 58~60
Raw material proportioning adjustment in bisphenol fluorene copolymerization aryl oxide succinamide prepared by embodiment 57, is prepared difference
The bisphenol fluorene of BFPPO contents is copolymerized aryl oxide succinamide, and specific data are shown in Table 15.
Table 15
Embodiment 61
By (395.2g, 0.95mol) bis- (4- fluorobenzoyls) decamethylene diamines (BFBD), (27.6g, 0.05mol) BFPPO,
(276g, 2mol) potassium carbonate, 200ml toluene, (352g, 1mol) 4,4'- diphenyl methylenes bis-phenol (also known as bisphenol b P, DHTPM)
Reaction vessel is added with 1500ml formamides, then under nitrogen protection, in 185 DEG C of dehydration 3h of temperature, then in temperature 200
DEG C reaction 8h, obtain sticky copolymer solution, above-mentioned solution be cooled to 120 DEG C, is poured into water while stirring, be precipitated grey
Fine strip shape polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use deionization respectively
Water, ethyl alcohol washing are copolymerized aryl oxide decanediamide in 100 DEG C of dry l0h of temperature to get to the bisphenol b P after purification containing BFPPO.
The intrinsic viscosity [η] of the copolymerization aryl oxide decanediamide is 0.75dL/g；Limit oxygen index is 26.5%；Vertical combustion
Grade is V-2, tensile strength 76MPa.
Embodiment 62~64
Raw material proportioning adjustment in bisphenol b P copolymerization aryl oxide decanediamides prepared by embodiment 61, is prepared difference
The bisphenol b P of BFPPO contents is copolymerized aryl oxide decanediamide, and specific data are shown in Table 16.
Table 16
Embodiment 65
By (315.4g, 0.95mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (27.6g, 0.05mol) BFPPO,
(276g, 2mol) potassium carbonate, 200ml toluene, (290g, 1mol) 4,4'- (1- phenethyls) bis-phenol (also known as bisphenol-ap, PEBP) and
Reaction vessel is added in 1500ml formamides, then under nitrogen protection, in 175 DEG C of dehydration 2.5h of temperature, then in temperature 200
DEG C reaction 8h, obtain sticky copolymer solution, above-mentioned solution be cooled to 120 DEG C, is poured into water while stirring, be precipitated grey
Fine strip shape polymer crude product；Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then use deionization respectively
Water, ethyl alcohol washing, aryl oxide succinamide is copolymerized in 100 DEG C of dry l0h of temperature to get to the bisphenol-ap after purification containing BFPPO.
The intrinsic viscosity [η] of the copolymerization aryl oxide succinamide is 0.82dL/g；Limit oxygen index is 29.5%；Vertical combustion
Grade is V-1, tensile strength 92MPa.
Embodiment 66~68
Raw material proportioning adjustment in bisphenol-ap copolymerization aryl oxide succinamide prepared by embodiment 65, is prepared difference
The bisphenol-ap of BFPPO contents is copolymerized aryl oxide decanediamide, and specific data are shown in Table 17.
Table 17
Embodiment 69~72
Bis- (4- fluorobenzoyls) butanediamine of raw material in bisphenol-ap copolymerization aryl oxide succinamide prepared by embodiment 65
(BFBB) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH) are replaced with, the adjustment of other raw material proportionings is shown in Table 18, difference is prepared
The bisphenol-ap of BFPPO contents is copolymerized aryl oxide adipamide.
Table 18
Comparative example 1
By (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene,
Reaction vessel is added in (350g, 1mol) 9,9- bis- (4- hydroxy phenyls) fluorenes (also known as bisphenol fluorene, FDP) and 1500ml formamides, so
Afterwards under nitrogen protection, in 185 DEG C of dehydration 2h of temperature, then in 200 DEG C of reaction 8h of temperature, it is molten to obtain sticky polymer
Above-mentioned solution is cooled to 120 DEG C, is poured into water while stirring by liquid, and grey fine strip shape polymer crude product is precipitated；It will be above-mentioned poly-
It closes object to wash through water, ethyl alcohol, in 80 DEG C of dry 8h, crush, then washed respectively with deionized water, ethyl alcohol, in 100 DEG C of dryings of temperature
L0h is to get to bisphenol fluorene polyarylether succinamide after purification.Specific data are shown in Table 19.
Comparative example 2
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol fluorene polyarylether succinamide prepared by comparative example 1
Amine (BFBB) replaces with (360g, 1mol) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH), be prepared bisphenol fluorene polyarylether oneself two
Amide.Specific data are shown in Table 19.
Comparative example 3
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol fluorene polyarylether succinamide prepared by comparative example 1
Amine (BFBB) replaces with (388g, 1mol) bis- (4- fluorobenzoyls) octamethylenediamines (BFBO), and bisphenol fluorene polyarylether pungent two is prepared
Amide.Specific data are shown in Table 19.
Comparative example 4
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol fluorene polyarylether succinamide prepared by comparative example 1
Amine (BFBB) replaces with (416g, 1mol) bis- (4- fluorobenzoyls) decamethylene diamines (BFBD), and the bisphenol fluorene polyarylether last of the ten Heavenly stems two is prepared
Amide.Specific data are shown in Table 19.
Table 19
Comparative example 5
By (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene,
(352g, 1mol) 4,4'- diphenyl methylenes bis-phenol (also known as bisphenol b P, DHTPM) and 1500ml N-methyl pyrrolidones are added anti-
Container is answered, then under nitrogen protection, in 170 DEG C of dehydration 3h of temperature, then in 200 DEG C of reaction 8h of temperature, is obtained sticky
Above-mentioned solution is cooled to 120 DEG C, is poured into water while stirring by polymer solution, and grey fine strip shape polymer crude product is precipitated；
Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then washed respectively with deionized water, ethyl alcohol, in temperature
100 DEG C of dry l0h are to get to bisphenol b P polyarylether succinamides after purification.Specific data are shown in Table 20.
Comparative example 6
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol b P polyarylether succinamides prepared by comparative example 5
Amine (BFBB) replaces with (360g, 1mol) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH), be prepared bisphenol b P polyarylethers oneself two
Amide.Specific data are shown in Table 20.
Comparative example 7
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol b P polyarylether succinamides prepared by comparative example 5
Amine (BFBB) replaces with (388g, 1mol) bis- (4- fluorobenzoyls) octamethylenediamines (BFBO), and bisphenol b P polyarylethers pungent two are prepared
Amide.Specific data are shown in Table 20.
Comparative example 8
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol b P polyarylether succinamides prepared by comparative example 5
Amine (BFBB) replaces with (416g, 1mol) bis- (4- fluorobenzoyls) decamethylene diamines (BFBD), and the bisphenol b P polyarylether last of the ten Heavenly stems two is prepared
Amide.Specific data are shown in Table 20.
Table 20
Comparative example 9
By (332g, 1mol) bis- (4- fluorobenzoyls) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene,
Reaction is added in (290g, 1mol) 4,4'- (1- phenethyls) bis-phenol (also known as bisphenol-ap, PEBP) and 1500ml N-methyl pyrrolidones
Then under nitrogen protection container in 170 DEG C of dehydration 3h of temperature, then in 200 DEG C of reaction 8h of temperature, obtains sticky gather
Above-mentioned solution is cooled to 120 DEG C, is poured into water while stirring by polymer solution, and white fine strip shape polymer crude product is precipitated；It will
Above-mentioned polymer is washed through water, ethyl alcohol, in 80 DEG C of dry 8h, is crushed, then washed respectively with deionized water, ethyl alcohol, in temperature 100
DEG C dry l0h is to get to bisphenol-ap polyarylether succinamide after purification.Specific data are shown in Table 21.
Comparative example 10
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol-ap polyarylether succinamide prepared by comparative example 9
Amine (BFBB) replaces with (360g, 1mol) bis- (4- fluorobenzoyls) hexamethylene diamines (BFBH), be prepared bisphenol-ap polyarylether oneself two
Amide.Specific data are shown in Table 21.
Comparative example 11
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol-ap polyarylether succinamide prepared by comparative example 9
Amine (BFBB) replaces with (388g, 1mol) bis- (4- fluorobenzoyls) octamethylenediamines (BFBO), and bisphenol-ap polyarylether pungent two is prepared
Amide.Specific data are shown in Table 21.
Comparative example 12
(332g, 1mol) bis- (4- fluorobenzoyls) fourths two in bisphenol-ap polyarylether succinamide prepared by comparative example 9
Amine (BFBB) replaces with (388g, 1mol) bis- (4- fluorobenzoyls) decamethylene diamines (BFBD), and the bisphenol-ap polyarylether last of the ten Heavenly stems two is prepared
Amide.Specific data are shown in Table 21.
Table 21
Claims (10)
1. a kind of intrinsic fire-retardant half aromatic co aryl oxide amide, it is characterized in that：The host molecule general structure of the polymer is：
Wherein：M, n are mole percent, m+n=100；
In any one.
2. intrinsic fire-retardant half aromatic co aryl oxide amide according to claim 1, it is characterised in that：
When n is 5-30mol%, i.e. Ar in formula one2Molar content be 2.5-15mol%, the semi-aromatic being prepared is total
The intrinsic viscosity [η] of polyarylether amide is 0.69-1.01dL/g, limit oxygen index 30.0-45.5%, UL-94 vertical combustion
Grade is V-2-V-0 grades, tensile strength 68-108MPa；
When n is 5-30mol%, i.e. R in formula two2Molar content be 2.5-15mol%, the semi-aromatic being prepared is total
The intrinsic viscosity [η] of polyarylether amide is 0.65-0.98dL/g, limit oxygen index 26.8-38.5%, UL-94 vertical combustion
Grade is stepless V-2-V-0 grades, tensile strength 65-105MPa.
3. intrinsic fire-retardant half aromatic co aryl oxide amide according to claim 1 or 2, it is characterised in that：Structure Ar1It comes from
Any one in following diphenol：
Structure Ar2Any one in following diphenol：
Any one of structure R1 in following semi-aromatic difluoro diamides：
Any one of structure R2 in following difluoro diamides：
4. a kind of preparation method of intrinsic fire-retardant half aromatic co aryl oxide amide as claimed in claim 3, it is characterised in that：
(1) when preparing the intrinsic fire-retardant half aromatic co aryl oxide amide as described in formula one, include the following steps：
In the reaction vessel, Ar is obtained described in being added1Diphenol DHTPM or any one of FDP or PEBP, described obtain
Ar2Diphenol DOPO-HQ or any one of 2DOPO-DMSi or 2DOPO-DPSi, described obtain R1Semi-aromatic difluoro
Diamides BFBB or BFBH or any one of BFBO or BFBD, catalyst, dehydrating agent, high boiling solvent are protected in inert gas
It under shield, heats up and certain temperature is kept to be reacted, obtain, containing the solution of the copolymer as described in formula one, after being purified, obtaining
To the intrinsic fire-retardant half aromatic co aryl oxide amide as described in formula one；
(2) when preparing the intrinsic fire-retardant half aromatic co aryl oxide amide as described in formula two, include the following steps：
In the reaction vessel, Ar is obtained described in being added1Diphenol DHTPM or any one of FDP or PEBP, described obtain
R2Any one of difluoro diamides BFBPSi or BFPPO, described obtain R1Semi-aromatic difluoro diamides BFBB or
BFBH or any one of BFBO or BFBD, catalyst, dehydrating agent, high boiling solvent heat up and protect under inert gas protection
It holds certain temperature to be reacted, obtains, containing the liquid of the copolymer as described in formula two, after being purified, obtaining as described in formula two
Intrinsic fire-retardant half aromatic co aryl oxide amide.
5. a kind of preparation method of intrinsic fire-retardant half aromatic co aryl oxide amide as claimed in claim 4, it is characterised in that：Add
What is entered described obtains Ar2Any diphenol account for overall reaction raw material molar content be 2.5-15mol%, addition it is described
Obtain R2Any difluoro diamides account for overall reaction raw material molar content be 2.5-15mol%.
6. a kind of preparation method of intrinsic fire-retardant half aromatic co aryl oxide amide as described in claim 4 or 5, feature exist
In：The reaction condition of the reaction is：Temperature control continues instead for 190-220 DEG C in 150-190 DEG C of dehydration 1-6h, in temperature
Answer 6-12h.
7. a kind of preparation method of intrinsic fire-retardant half aromatic co aryl oxide amide as claimed in claim 6, it is characterised in that：
The catalyst is one kind in sodium carbonate, potassium carbonate, cesium carbonate；
The dehydrating agent is one kind in toluene, ethylbenzene, ortho-xylene, meta-xylene, paraxylene；
The inert gas is one kind in nitrogen, argon gas；
High boiling solvent is one kind in formamide, acetamide, N-Methyl pyrrolidone, sulfolane.
8. a kind of preparation method of intrinsic fire-retardant half aromatic co aryl oxide amide as described in claim 4 or 5 or 7, feature
It is：Phosphorous/silicon the diphenol 2DOPO-DMSi or 2DOPO-DPSi for obtaining Ar2 is prepared by following steps：
It is molten by 10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxides (DOPO-HQ) in reaction vessel
Solution in organic solvent keeps that dichlorosilane solution is added dropwise when certain temperature；It also needs to that acid binding agent is added, acid binding agent can be three
Ethamine；After dichlorosilane is added dropwise, holding is reacted at a certain temperature, is generated containing the phosphorous/silicon diphenol
Reaction solution after being purified, obtains the phosphorous/silicon diphenol.
9. a kind of preparation method of intrinsic fire-retardant half aromatic co aryl oxide amide as described in claim 4 or 5 or 7, feature
It is：Siliceous or phosphorous difluoro the diamides BFBPSi or BFPPO for obtaining R2 is prepared by following steps：It will contain
Silicon diamines or phosphorous diamines, room-temperature dissolution is in dichloromethane；In the reaction vessel, dichloromethane is added, it then will be to fluorine
Chlorobenzoyl chloride is dissolved in dichloromethane, and the good siliceous diamines of above-mentioned configuration or phosphorous diamine solution is then added；It also needs to
Acid binding agent is added, acid binding agent can be triethylamine；After diamine solution drips, the reaction was continued at room temperature a period of time, raw
At the reaction solution containing the siliceous or phosphorous difluoro diamides, after being purified, the siliceous or phosphorous difluoro is obtained
Diamides.
10. a kind of preparation method of intrinsic fire-retardant half aromatic co aryl oxide amide as claimed in claim 8, it is characterised in that：
The organic solvent is at least one of formamide, dimethylformamide, dimethylacetylamide.
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| CN109880078A (en) * | 2018-12-29 | 2019-06-14 | 福建师范大学泉港石化研究院 | A kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone and preparation method thereof |
| WO2020132929A1 (en) * | 2018-12-26 | 2020-07-02 | 广东生益科技股份有限公司 | Phosphorous and silicon containing flame retardant, preparation method therefor, flame retardant resin composition, prepreg and metal foil-cladding laminate |
| CN111363339A (en) * | 2018-12-26 | 2020-07-03 | 广东生益科技股份有限公司 | Phosphorus-silicon-containing flame retardant, preparation method thereof, flame-retardant resin composition, prepreg and metal-foil-clad laminate |
| CN114716664A (en) * | 2022-04-22 | 2022-07-08 | 四川大学 | Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof |
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| WO2020132929A1 (en) * | 2018-12-26 | 2020-07-02 | 广东生益科技股份有限公司 | Phosphorous and silicon containing flame retardant, preparation method therefor, flame retardant resin composition, prepreg and metal foil-cladding laminate |
| CN111363339A (en) * | 2018-12-26 | 2020-07-03 | 广东生益科技股份有限公司 | Phosphorus-silicon-containing flame retardant, preparation method thereof, flame-retardant resin composition, prepreg and metal-foil-clad laminate |
| CN109880078A (en) * | 2018-12-29 | 2019-06-14 | 福建师范大学泉港石化研究院 | A kind of thin-walled high temperature resistant radiation hardness fire-resistant cable material polyether-ether-ketone and preparation method thereof |
| CN114716664A (en) * | 2022-04-22 | 2022-07-08 | 四川大学 | Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof |
| CN114716664B (en) * | 2022-04-22 | 2023-02-28 | 四川大学 | Semi-aromatic copolymerized polyarylether amide, complex thereof and preparation method thereof |
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