CN109679090A - A kind of poly(aryl ether ketone) and its synthetic method containing nitrogen, sulphur cooperative flame retardant material - Google Patents
A kind of poly(aryl ether ketone) and its synthetic method containing nitrogen, sulphur cooperative flame retardant material Download PDFInfo
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- CN109679090A CN109679090A CN201811635915.4A CN201811635915A CN109679090A CN 109679090 A CN109679090 A CN 109679090A CN 201811635915 A CN201811635915 A CN 201811635915A CN 109679090 A CN109679090 A CN 109679090A
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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
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
- C08G65/4025—(I) or (II) containing fluorine other than 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
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
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Abstract
The invention discloses a kind of poly(aryl ether ketone) and its synthetic method containing nitrogen, sulphur cooperative flame retardant material.It is x:(1~x that this method will contain methyl bisphenol, dihydric phenol, difluoro benzophenone and catalyst in molar ratio): 1:(1.2~2) it is placed in solvent, in N2Prior to 130~150 DEG C 1~5h of reaction in gas are obtained then at 150~175 DEG C of 3~20h of reaction and are replaced poly(aryl ether ketone) containing methyl.Resulting poly(aryl ether ketone) must contain bromomethylation poly aryl ether ketone polymer through N- bromo-succinimide bromomethylation, and poly aryl ether ketone polymer containing bromomethylation reacts poly aryl ether ketone polymer of the synthesis containing nitrogen, sulphur cooperative flame retardant material with 5- sulfydryl -1- methyl tetrazolium.This method is simple and easy to do, synthesizes the poly(aryl ether ketone) CABLE MATERIALS resin containing nitrogen, sulphur cooperative flame retardant material at salt with weak base in the polymerization.The CABLE MATERIALS resin 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, pollution-free, halogen-free flameproof, 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 poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material that the present invention relates to a kind of, and in particular to one kind is assisted containing nitrogen, sulphur
With the ketone-grouped resin and its synthetic method of fire proofing.
Background technique
As the range that power cable is applied is more and more wider, different use environments have a different requirements, e.g., high temperature resistant, resistance to low
Temperature, oil resistant, tear-proof, fire-retardant etc..Especially in the case where use condition is special, application environment is complicated, the need of special cable
Ask day it is aobvious protrude, to reliability, the durability of cable, more stringent requirements are proposed.China express railway and urban track traffic dress
Standby to quickly grow, requirement of the manufacturing enterprise to high-speed rail and urban rail dress cable in stock is towards ultra-thin-wall, high-temperature resistant, high oil resistant, high resistant
Combustion direction is developed.The insulating wall thickness of common thin-walled cable is in 0.3mm or more, and institute is equipped in high-speed railway and urban track traffic
The ultra-thin-wall insulated cable insulation wall thickness needed requires to be 0.18mm.Currently, the primary insulation material of cable industry production thin-walled cable
Material is cross-linked polyolefin, due in the CABLE MATERIALS contain more fire retardant, insulation resistance is smaller, cable be easy it is breakdown, and
And the physical mechanical property of cable, there are many deficiencies, insulation wall can not achieve ultra-thin, it is difficult to meet the needs of manufacturing enterprise.Cause
This, production high-temperature resistant, high oil resistant, high fire-retardance a key technology of ultra-thin-wall insulated cable be exactly to study suitable cable
Material.
Nitrogenated flame retardant is a kind of novel halogen-free flame retardants, has Halogen, low toxicity, low cigarette, corrosion-free, divides desorption heat energy
Generate non-flammable gases, to heat and UV stable, it is at low cost the advantages that.Exploitation is high with nitrogen content, thermal stability is good, high temperature
The distributed and matched nitrogenated flame retardant of polymer phase has become when previous important topic.
High poly- type organic phosphine fire retardant include molecular weight is big, phosphorus content is high, with the compatibility of material is good, migration is small plus
The advantages that work performance is good, excellent fireproof performance, the fire retardant of two kinds of ignition-proof elements of sulfur-bearing and phosphorus is more fire-retardant than independent phosphorus element-containing
Agent has better flame retardant effect.Considered based on the above advantage, this paper synthesizes a series of products, contains association in molecular structure
With fire-retardant sulphur and more P elements, the introducing of sulphur atom strengthens acid source and gas source, accelerates matrix carbonization to reach fire-retardant
Purpose, and then enhance flame retardant effect.Also contain stable fragrant phosphine key in structure simultaneously, so that fire-retardant matrix is in heated process
In be readily formed fine and close and uniform polyphosphoric acid protective film.A series of sulfur-bearing organic phosphine fire retardants of this paper studies synthesis,
Have the characteristics that structure novel, phosphorus content it is high, with the compatibility of material is good, excellent fireproof performance, processing performance are good, be to hinder at present
Fire a new topic of developing of agent research field.
Multielement synergetic organic nitrogen, sulphur fire retardant are due to assigning the better processing performance of material, by nitrogenous, sulphur fire retardant
In the form of polymer monomer, or as the chemical reaction of substituent group monomer participation high polymer, become Polymer Structure after reaction
A part, so that material be made to reach fire-retardant purpose.Have many advantages, such as simple process, it is wide in variety, have a wide range of application, the mistake used
Also solved in journey the compatibility of fire proofing and substrate, dispersibility, it is interface characteristics the problems such as.
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.Nitrogenous, sulphur fire retardant is introduced poly(aryl ether ketone) side by nucleophilic substitution
Prepare nitrogenous, sulphur fire proofing poly(aryl ether ketone) new varieties in chain, the resinoid have simultaneously poly(aryl ether ketone) high temperature resistant, it is corrosion-resistant,
Radiation hardness and fire-retardant advantage.With active copper atom or copper ion a kind of chemisorption can occur for nitrogen, sulphur, or occur in turn
Chelation firmly safeguards film to form one layer of densification, and equipment made of copper is made to obtain good maintenance.
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 nitrogen, sulphur collaboration resistance
The synthetic method of the poly(aryl ether ketone) of combustible material.
The present invention is achieved through the following technical solutions:
A kind of poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material, it is characterised in that structure are as follows:
Wherein, x are as follows: 5~200, y are as follows: (40-x)~(200-x), and (x+y) is 40~200.
Another aspect of the present invention is intended to disclose a kind of synthesis side of poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material
Method, the synthetic method include the following steps:
(1) will contain methyl bisphenol, dihydric phenol, difluoro benzophenone and catalyst is x:y:(x+y in molar ratio): (x+y) ×
(1.2~2) are placed in organic solvent I, in N2Prior to 130~150 DEG C 1~5h of reaction under airflow function, then at 150~175 DEG C
3~20h is reacted, poly(aryl ether ketone) containing methyl is synthesized；
(2) poly(aryl ether ketone) containing methyl obtained by step (1) is dissolved in organic solvent II, oil-soluble initiator causes, and NBS is
Bromide reagent is cooled to room temperature to reaction system after reacting 4~7h under the conditions of 70~130 DEG C, reaction solution is precipitated in right amount
In ethyl alcohol, by Soxhlet extractor, rope is mentioned for 24 hours in acetone after filtering, and vacuum drying obtains the polymerization of bromomethylation poly(aryl ether ketone)
Object；
(3) in molar ratio by bromomethylation poly(aryl ether ketone), nitrogenous and sulphur organic compound and catalyst obtained by step (2)
(the ratio between bromomethyl unit molal quantity and nitrogenous, sulphur organic compound molal quantity in poly(aryl ether ketone)) is 1:(1.0~2.0): (1.0
~2.0) it × 1.2 is placed in organic solvent III, in 30~80 DEG C of 1~8h of reaction, synthesizes containing nitrogen, sulphur cooperative flame retardant material
Poly(aryl ether ketone).
Wherein, the nitrogenous and sulphur organic compound in step (3) is 2-mercaptobenzimidazole, 2-mercaptothiazoline, 2- mercapto
Base -1,3,4- thiadiazoles, 2- sulfydryl -5- methyl-1,3,4- thiadiazoles or 5- (difluoro-methoxy) -2- sulfydryl -1H- benzo miaow
Azoles；
In step (1) is adjacent methyl hydroquinone, 2,3- dimethyl hydroquinones, 2,5- dimethyl pair containing methyl bisphenol
Benzenediol, 2,6- dimethyl hydroquinones, 2,3,5-trimethylhydroquinone, 2,3,5,6- duroquinols, tetramethyl
'-biphenyl diphenol or hexafluoro bisphenol-a；
Dihydric phenol in step (1) is hydroquinone, resorcinol, bisphenol fluorene, hexafluoro bisphenol-a, bisphenol-A or '-biphenyl diphenol
In any one or any two kinds or more combination；
Catalyst in step (1) and (3) is Anhydrous potassium carbonate or natrium carbonicum calcinatum；
Organic solvent I in step (1) or (3) is toluene and n,N-dimethylacetamide, dimethyl sulfoxide or N- methyl pyrrole
The combination of any one or any two kinds or more in pyrrolidone；
Organic solvent II in step (2) is any one of methylene chloride, dichloroethanes or chloroform；
Oil-soluble initiator in step (2) is azodiisobutyronitrile, benzoyl peroxide or cumyl peroxide
Any one.
Organic solvent III in step (3) is in n,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone
Any one.
Compared with the existing technology, the invention has the advantages that and the utility model has the advantages that
(1) it is easy to for nitrogenous, sulphur organic compound being introduced into poly(aryl ether ketone) side group with the present invention, this method weak base
At salt, the problems such as NaOH degradable at product caused by salt, reaction difficult to control and alkali pollution are used in industry is overcome, height is made
Molecular weight contains nitrogen, sulphur poly(aryl ether ketone), and the equal relative molecular mass of number is between 2-10 ten thousand.
(2) nitrogenous, sulphur organic compound is introduced in poly(aryl ether ketone) side group, is still able to maintain the heat-resisting quantity of poly(aryl ether ketone) main chain
Can, containing two kinds of nitrogen, sulphur ignition-proof elements, play double fire retardant effect.
(3) present invention applies nucleophilic substitution, and 5- sulfydryl -1- methyl tetrazolium etc. is nitrogenous, sulphur organic compound introduces
The poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material is synthesized in poly(aryl ether ketone) strand, has intensity height, electrical insulating property good, and
With the characteristics such as low cigarette, Halogen, fire-retardant, it is very suitable to ultra-thin-wall cable extrusion, is able to satisfy the processing work of ultra-thin-wall insulated cable
Skill and product technology requirement, convenient for production, with good economic efficiency and promotional value.
Figure of description explanation
Fig. 1 be poly(aryl ether ketone) (PEEK), bromomethylation poly(aryl ether ketone) and contain nitrogen, sulphur cooperative flame retardant material poly(aryl ether ketone)
's1H-NMR spectrum (CDCl3) wherein, it (b) is bromomethylation poly(aryl ether ketone) that (a), which is poly(aryl ether ketone), (c) is to contain nitrogen, sulphur collaboration
Fire proofing poly(aryl ether ketone).
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
It is sequentially added in three-necked flask containing 2,4- dimethyl hydroquinones 1.3814g (10mmol), hexafluoro bisphenol-a
10.0686g (30mmol), difluoro benzophenone 8.7280g (40mmol), Anhydrous potassium carbonate 6.6332g (48mmol), toluene
160mL, DMAc200mL, in the N of 1mL/s2140 DEG C of reaction 3h are flowed down, 175 DEG C of reaction 6h are then heated to, immediately by reaction solution
It pours into deionized water and precipitates under stiring, filter.The sediment being obtained by filtration is impregnated with deionized water, is impregnated in running water
It filters afterwards for 24 hours, puts the precipitate in dry 10h in 80 DEG C of vacuum drying ovens, obtain product and contain methyl substituents poly(aryl ether ketone).GPC
Analysis, Mn=20200, PDI=1.84.
It weighs above-mentioned steps products therefrom and contains methyl substituents poly(aryl ether ketone) 10.0g and be dissolved in the dried tetrachloro of 200mL
Change in carbon.Polymer be added after being completely dissolved NBS (3.8576g, 10.8mmol) and BPO (0.1312g, 0.540mmol) in
The reaction was continued under the conditions of 90 DEG C 4h.After reaction system is cooled to room temperature, reaction solution is precipitated in 100mL ethyl alcohol, after filtering
By Soxhlet extractor, rope is mentioned for 24 hours in acetone, and vacuum drying obtains bromomethylation poly(aryl ether ketone).1HNMR analysis, the bromine of methyl
Rate is 90.2%.
Above-mentioned steps products therefrom bromomethylation poly(aryl ether ketone) 10.0g is weighed, 5- (difluoro-methoxy) -2- sulfydryl-is added
1H- benzimidazole 3.8456g and Na2CO32.6418g is dissolved in alkyl pyrrolidone, prior to 40 DEG C reaction 1h, anti-then at 50 DEG C
3h is answered, the poly(aryl ether ketone) for synthesizing containing nitrogen, sulphur cooperative flame retardant material.Gpc analysis, Mn=22544, PDI=2.21.
Embodiment 2
It is sequentially added in three-necked flask containing neighbour methyl hydroquinone 0.4966g (4mmol), bisphenol fluorene 12.6148g
(36mmol), difluoro benzophenone 8.7280g (40mmol), Anhydrous potassium carbonate 6.6332g (48mmol), toluene 160mL, DMAc
200mL, in the N of 1mL/s2140 DEG C of reaction 3h are flowed down, 170 DEG C of reaction 7h is then heated to, immediately falls reaction solution under stiring
Enter in deionized water and precipitate, filters.The sediment being obtained by filtration is impregnated with deionized water, impregnates in running water and filters afterwards for 24 hours, it will
Sediment is placed in 80 DEG C of vacuum drying ovens dry 10h, obtains product and contains methyl substituents poly(aryl ether ketone).Gpc analysis, Mn=
23960, PDI=1.98.
It weighs and is dissolved in the dried carbon tetrachloride of 200mL containing methyl substituents poly(aryl ether ketone) 10.0g obtained by above-mentioned steps
In.Polymer be added after being completely dissolved NBS0.7218g (4.0mmol) and dicumyl peroxide 0.0612g (0.20mmol) in
The reaction was continued under the conditions of 135 DEG C 5h.After reaction system is cooled to room temperature, reaction solution is precipitated in 200mL ethyl alcohol, it is filtered
By Soxhlet extractor, rope is mentioned for 24 hours in acetone afterwards, and vacuum drying obtains bromomethylation poly(aryl ether ketone).1HNMR analysis, methyl
Bromination rate is 98.6%.
Weigh bromomethylation poly(aryl ether ketone) 10.0g, 5- (difluoro-methoxy) -2- sulfydryl -1H- benzo miaow obtained by above-mentioned steps
Azoles 0.6422g, Na2CO30.4919g is dissolved in DMAc, in 50 DEG C of reaction 5h, synthesize containing nitrogen, sulphur cooperative flame retardant material it is poly-
Aryl ether ketone.Gpc analysis, Mn=24980, PDI=2.28.
Embodiment 3
S1: it the synthesis of poly(aryl ether ketone): is sequentially added in three-necked flask containing adjacent methyl hydroquinone 1.2414g
(10mmol), hexafluoro bisphenol-a 10.0868g (30mmol), difluoro benzophenone 8.7280g (40mmol), Anhydrous potassium carbonate
6.6332g (48mmol), toluene 160mL, DMAc200mL, in the N of 1mL/s2140 DEG C of reaction 3h are flowed down, then heat to 170
DEG C reaction 8h, reaction solution is poured into deionized water under stiring precipitate immediately, filter.By the sediment being obtained by filtration spend from
Sub- water impregnates, and impregnates in running water and filters afterwards for 24 hours, puts the precipitate in dry 10h in 80 DEG C of vacuum drying ovens, obtains product and contain methyl
Substituent group poly(aryl ether ketone).Gpc analysis, Mn=20200, PDI=1.84.
S2: it the synthesis of Bromomethyl Substituted poly(aryl ether ketone): weighs 10.0g poly(aryl ether ketone) and is dissolved in four dried chlorinations of 200mL
In carbon.NBS (1.9288g, 5.4mmol) is added in polymer after being completely dissolved and 85 DEG C of BPO (0.0656g, 0.270mmol) anti-
Answer 7h.After reaction system is cooled to room temperature, reaction solution is precipitated in 200mL ethyl alcohol, is existed after filtering by Soxhlet extractor
Rope mentions for 24 hours in acetone, and vacuum drying obtains bromomethylation poly(aryl ether ketone).1HNMR analysis, the bromination rate of methyl are 90.2%.
S3: 10.0g bromomethylation poly(aryl ether ketone), 0.9511g 2- sulfydryl -1,3,4- thiadiazoles and 0.916g are weighed
Na2CO3It is dissolved in solvent, in 60 DEG C of reaction 4h, the poly(aryl ether ketone) for synthesizing containing nitrogen, sulphur cooperative flame retardant material.Gpc analysis, Mn
=21480, PDI=2.11.
Embodiment 4
The synthesis of methyl substituents poly(aryl ether ketone): it is sequentially added in three-necked flask containing 2,4- dimethyl hydroquinones
2.7632g (20mmol), '-biphenyl diphenol 3.7242g (20mmol), difluoro benzophenone 8.7280g (40mmol), Carbon Dioxide
Potassium 6.6332g (48mmol), toluene 160mL, DMAc 200mL, in the N of 1mL/s2140 DEG C of reaction 3h are flowed down, are then heated to
170 DEG C of reaction 8h, reaction solution is poured into deionized water precipitate immediately under stiring, filtering.The sediment being obtained by filtration is used
Deionized water is impregnated, and is impregnated in running water and is filtered afterwards for 24 hours, is put the precipitate in dry 10h in 80 DEG C of vacuum drying ovens, is obtained product and contain
Methyl substituents poly(aryl ether ketone).
The synthesis of Bromomethyl Substituted poly(aryl ether ketone): it weighs 10.0g poly(aryl ether ketone) and is dissolved in the dried carbon tetrachloride of 200mL
In.NBS (8.5700g, 48mmol) is added in polymer after being completely dissolved and 85 DEG C of BPO (0.5814g, 0.24mmol) are continued instead
Answer 5h.After reaction system is cooled to room temperature, reaction solution is precipitated in 200mL ethyl alcohol, is existed after filtering by Soxhlet extractor
Rope mentions for 24 hours in acetone, and vacuum drying obtains bromomethylation poly(aryl ether ketone).1HNMR analysis, the bromination rate of methyl are 99.6%.
Weigh 10.0g bromomethylation poly(aryl ether ketone), 2.0975g 2-mercaptothiazoline and 2.0801g 2- sulfydryl -1,3,4-
Thiadiazoles and 2.5348g Na2CO3Be dissolved in DMAc, in 50 DEG C of reaction 6h, synthesize containing nitrogen, sulphur cooperative flame retardant material it is poly-
Aryl ether ketone.Gpc analysis, Mn=29690, PDI=2.31.
Embodiment 5
The synthesis of methyl substituents poly(aryl ether ketone): it is sequentially added in three-necked flask containing 2,4- dimethyl hydroquinones
2.7628g (20mmol), hexafluoro bisphenol-a 6.7246g (20mmol), difluoro benzophenone 8.7280g (40mmol), anhydrous carbon
Sour potassium 6.6332g (48mmol), toluene 160mL, DMAc200mL, in the N of 1mL/s2140 DEG C of reaction 3h are flowed down, are then heated to
170 DEG C of reaction 6h, reaction solution is poured into deionized water precipitate immediately under stiring, filtering.The sediment being obtained by filtration is used
Deionized water is impregnated, and is impregnated in running water and is filtered afterwards for 24 hours, is put the precipitate in dry 10h in 80 DEG C of vacuum drying ovens, is obtained product and contain
Methyl substituents poly(aryl ether ketone).
The synthesis of Bromomethyl Substituted poly(aryl ether ketone): it weighs 10.0g poly(aryl ether ketone) and is dissolved in the dried carbon tetrachloride of 200mL
In.NBS (8.5700g, 48mmol) and 80 DEG C of BPO (0.5814g, 0.24mmol) reactions is added in polymer after being completely dissolved
8h.After reaction system is cooled to room temperature, by mixture precipitation into 100mL ethyl alcohol, by Soxhlet extractor third after filtering
Rope mentions for 24 hours in ketone, and vacuum drying obtains bromomethylation poly(aryl ether ketone).
Weigh 10.0g bromomethylation poly(aryl ether ketone), 2.1661g 2-mercaptobenzimidazole and 1.9928g 2- sulfydryl -5- first
Base -1,3,4- thiadiazoles and 2.5348g Na2CO3It is dissolved in solvent, in 80 DEG C of reaction 2h, synthesizes to contain nitrogen, sulphur cooperative flame retardant
The poly(aryl ether ketone) of material.Gpc analysis, Mn=32755, PDI=2.35.
Claims (11)
1. a kind of poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material, it is characterised in that the poly(aryl ether ketone) has following chemistry
Structural formula:
X are as follows: 5~200, y are as follows: (40-x)~(200-x).
2. a kind of poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material according to claim 1, it is characterised in that: 40≤
(x+y)≤200。
3. a kind of synthetic method of the poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material, it is characterised in that the synthetic method packet
Include following steps:
(1) will contain methyl bisphenol, dihydric phenol, difluoro benzophenone and catalyst is x:y:(x+y in molar ratio): (x+y) × (1.2
~2) it is placed in organic solvent I, in N2Prior to 130~150 DEG C 1~5h of reaction under airflow function, then at 150~175 DEG C of reactions 3
~20h synthesizes poly(aryl ether ketone) containing methyl；
(2) poly(aryl ether ketone) containing methyl obtained by step (1) is dissolved in organic solvent II, oil-soluble initiator causes, and NBS is bromination
Reagent is cooled to room temperature to reaction system after reacting 4~7h under the conditions of 70~130 DEG C, reaction solution is precipitated to ethanol in proper amount
In, by Soxhlet extractor, rope is mentioned for 24 hours in acetone after filtering, and vacuum drying obtains bromomethylation poly aryl ether ketone polymer；
(3) weigh bromomethylation poly(aryl ether ketone) obtained by step (2), by it with nitrogenous and sulphur organic compound, catalyst by mole
Than for 1:(1.0~2.0): (1.0~2.0) × 1.2 are placed in organic solvent III, and 30~80 DEG C of 1~8h of reaction synthesize to contain
The poly(aryl ether ketone) of nitrogen, sulphur cooperative flame retardant material.
4. a kind of synthetic method of poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material according to claim 3, feature
It is: the nitrogenous and sulphur organic compound in the step (3) are as follows: 2-mercaptobenzimidazole, 2-mercaptothiazoline, 2- sulfydryl-
1,3,4- thiadiazoles, 2- sulfydryl -5- methyl-1,3,4- thiadiazoles or 5- (difluoro-methoxy) -2- sulfydryl -1H- benzimidazole.
5. a kind of synthetic method containing nitrogen, the ketone-grouped resin of sulphur cooperative flame retardant material according to claim 3,
It is characterized in that containing described in step (1) methyl bisphenol as adjacent methyl hydroquinone, 2,3- dimethyl hydroquinones, 2,5- dimethyl
Hydroquinone, 2,6- dimethyl hydroquinones, 2,3,5-trimethylhydroquinone, 2,3,5,6- duroquinols, tetramethyl
Base '-biphenyl diphenol or hexafluoro bisphenol-a.
6. a kind of synthetic method of poly(aryl ether ketone) containing nitrogen, sulphur cooperative flame retardant material according to claim 3, feature
It is that dihydric phenol described in step (1) is hydroquinone, resorcinol, bisphenol fluorene, hexafluoro bisphenol-a, bisphenol-A or biphenyl two
Phenol.
7. the synthetic method of the poly(aryl ether ketone) according to claim 3 containing nitrogen, sulphur cooperative flame retardant material, it is characterised in that
Catalyst described in step (1) and (3) is Anhydrous potassium carbonate or natrium carbonicum calcinatum.
8. the synthetic method of the poly(aryl ether ketone) according to claim 3 containing nitrogen, sulphur cooperative flame retardant material, it is characterised in that
Organic solvent I in step (1) be toluene with it is any in n,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone
A kind of or any two kinds or more of combination.
9. the synthetic method of the poly(aryl ether ketone) according to claim 3 containing nitrogen, sulphur cooperative flame retardant material, it is characterised in that
Step (2) organic solvent II is any one of methylene chloride, dichloroethanes or chloroform.
10. the synthetic method of the poly(aryl ether ketone) according to claim 3 containing nitrogen, sulphur cooperative flame retardant material, feature exist
Organic solvent III in step (3) is any one in n,N-dimethylacetamide, dimethyl sulfoxide or N-Methyl pyrrolidone
Kind.
11. the synthetic method of the poly(aryl ether ketone) according to claim 3 containing nitrogen, sulphur cooperative flame retardant material, feature exist
In step (2) oil-soluble initiator be azodiisobutyronitrile, benzoyl peroxide or cumyl peroxide it is any one
Kind.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811635915.4A CN109679090A (en) | 2018-12-29 | 2018-12-29 | A kind of poly(aryl ether ketone) and its synthetic method containing nitrogen, sulphur cooperative flame retardant material |
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| CN114516956A (en) * | 2021-12-17 | 2022-05-20 | 久耀电子科技（江苏）有限公司 | Preparation method of organosilane-modified intrinsic flame-retardant polyphenyl ether |
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