CN113292718A - Flame-retardant polyarylether composition - Google Patents
Flame-retardant polyarylether composition Download PDFInfo
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the technical field of communication materials, and particularly relates to a flame-retardant polyarylether-based composition. According to the invention, any one or both of the double-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer and the multi-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer are used as main resin, so that the prepreg and the copper clad laminate prepared from the flame-retardant polyarylether composition can also ensure sufficient overall performance and better flame-retardant performance when only a small amount of flame retardant is used or even no flame retardant is used in the flame-retardant polyarylether composition.
Description
Technical Field
The invention belongs to the technical field of communication materials, and particularly relates to a flame-retardant polyarylether-based composition.
Background
The copper-clad plate is widely applied to the fields of mobile phones, computers, wearable equipment, communication base stations, satellites, unmanned automobiles, unmanned aerial vehicles, intelligent robots and the like, and is one of key materials in electronic communication and information industries. The traditional thermosetting resin represented by epoxy resin, phenolic resin and cyanate resin has the advantages of high thermo-mechanical property, high quality, low price, convenient processing and strong universality, and is a common material for manufacturing copper-clad plate base materials. Researchers search continuously, optimize formula composition and process parameters, prepare various thermosetting copper-clad plates with qualified comprehensive performance, and meet the most basic requirements of each subdivision field of the electronic communication industry on the copper-clad plates.
However, in the above system, a large amount of flame retardant is always required to be introduced to make the copper clad laminate substrate have a good flame retardant effect. The introduction of a large amount of inorganic flame retardants can cause various problems of poor dispersibility of materials in the plate matrix, poor mechanical properties, poor uniformity and reliability of the plate properties and the like; although the compatibility between the small-molecular organic flame retardant and the matrix resin is better than that of the inorganic flame retardant, under the condition of high filling amount, the small-molecular organic flame retardant and the matrix resin not only can reduce the thermal deformation temperature and the mechanical strength of the board, but also can affect the CAF resistance, the dielectric property, the stability and the like of the copper-clad plate due to uncontrollable migration activity in the board.
Therefore, no matter the copper-clad plate substrate adopts an inorganic flame retardant or a small-molecular organic flame retardant, the key for improving the overall performance of the final copper-clad plate is to reduce the using amount of the flame retardant, so that the market urgently needs a copper-clad plate substrate with low flame retardant content, but the flame retardant performance can still meet the daily use requirement.
The patent publication No. CN112442079A, the Chinese patent of publication No. 2021.03.05, discloses a preparation method of a phosphorus-containing reactive flame retardant epoxy resin composition, a copper-clad plate and a flame retardant, wherein the phosphorus-containing reactive flame retardant is obtained by an addition reaction of a compound with a-P-H reactive group and a compound containing a carbon-nitrogen unsaturated bond.
However, the composition for copper clad laminate in the patent of the invention aims to improve the flame retardant property, the adopted method is to improve the flame retardant, but the dosage is relatively higher, so that the final copper clad laminate only improves the flame retardant property, and the parameters or properties of the dispersibility, the mechanical property, the uniformity and the reliability of the final copper clad laminate can not be well guaranteed, and the overall performance of the final copper clad laminate at least can not meet the current requirements of high-frequency and high-speed communication.
Disclosure of Invention
The invention provides a flame-retardant polyarylether-based composition, which can achieve the effect that when only a small amount of flame retardant is used in the flame-retardant polyarylether-based composition or even the flame retardant is not used, the prepared prepreg and copper-clad plate can also ensure enough overall performance and better flame-retardant performance by using any one or both of double-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer and multi-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer as main resin.
The technical scheme adopted by the invention for solving the problems is as follows: the flame-retardant polyarylether composition comprises main body resin, wherein the main body resin comprises any one or both of double-hydroxyl-terminated phosphorus-bromine-containing polyarylether oligomer and multi-hydroxyl-terminated phosphorus-bromine-containing polyarylether oligomer.
The further preferred technical scheme is as follows: the double-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer has the structure
The structure of the multi-hydroxyl type phosphorus bromine-containing polyarylether oligomer is
Or
Or
Or
Wherein T is hydroxy, L1Is structured as
R1-R4Each independently represents a C1-C12 hydrocarbon chain or aryl group.
The further preferred technical scheme is as follows: the main resin also comprises any one or both of a double-end hydroxyl type common polyarylether oligomer and a multi-end hydroxyl type common polyarylether oligomer.
The further preferred technical scheme is as follows: the structure of the double-end hydroxyl type common polyarylether oligomer is
Or
The structure of the multi-end hydroxyl type common polyarylether oligomer is
Or
Or
Wherein R is1-R4Each independently represents a C1-C12 hydrocarbon chain or aryl group, R5-R12、R14-R21、R23-R34、R37-R44And R47-R62Each independently represents H, C1-C12 carbon hydrocarbon chain, aryl or halogen, R22、R45And R46Each independently represents H or a C1-C12 hydrocarbon chain, R13、R35And R36Each independently represents any one of the following functional groups
Wherein R is63-R68Each independently represents a C1-C12 hydrocarbon chain or an aryl group.
The further preferred technical scheme is as follows: the main resin comprises double-hydroxyl-group type phosphorus-bromine-containing polyarylether oligomers, multi-hydroxyl-group type phosphorus-bromine-containing polyarylether oligomers, double-hydroxyl-group type common polyarylether oligomers and multi-hydroxyl-group type common polyarylether oligomers, wherein the double-hydroxyl-group type common polyarylether oligomers and the multi-hydroxyl-group type common polyarylether oligomers account for 50-99wt% of the total amount of the four hydroxyl-group-containing polyarylether oligomers; the ratio of the double-hydroxyl-terminated type phosphorus-bromine-containing polyarylether oligomer to the multi-hydroxyl-terminated type phosphorus-bromine-containing polyarylether oligomer is 2:8-7: 3; the ratio of the bi-hydroxyl-terminated common polyarylether oligomer to the multi-hydroxyl-terminated common polyarylether oligomer is 1:9-8: 2.
The further preferable technical scheme is that the preparation method of the hydroxyl-terminated polyarylether oligomer sequentially comprises the following steps:
s1, adding phenol into the homogeneous organic solution of the polyarylether, stirring and mixing, adding the peroxide radical initiator in batches, continuously stirring for 6-72 hours, and finally performing redistribution reaction on the chains of the polyarylether to obtain a primary system;
s2, adding a poor solvent of polyarylether into the initial system for the first time, stirring to separate out high molecular weight polyarylether which cannot undergo chain redistribution reaction, filtering to remove the precipitate, adding more poor solvent of polyarylether into the filtrate than the amount of polyarylether added for the first time, continuously stirring and mixing to separate out oligomer, and finally filtering, washing and drying in sequence to obtain the hydroxyl-terminated polyarylether oligomer
The further preferred technical scheme is as follows: the number average molecular weight of the polyarylether is 8000-50000, and the structure is
The solvent of the homogeneous organic solution is any one or a mixture of toluene, xylene and N, N-dimethylformamide; the phenol consists of four types of common bisphenol, common polyphenol, phosphorus bromine-containing bisphenol and phosphorus bromine-containing polyphenol; the peroxide free radical initiator is any one or a mixture of two of dibenzoyl peroxide or tert-butyl peroxybenzoate; the poor solvent is any one or a mixture of more of methanol, ethanol, isopropanol, butanol, ether or ester, and the common bisphenol has a structure of
The common polyphenol has the structure of
The structure of the phosphorus bromine-containing bisphenol is
or
Bromide of 10- (2, 9-dihydroxynaphthyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide,
or
Bromide of 2-diphenylphosphinyl-1, 4-benzenediol;
the structure of the phosphorus and bromine containing polyphenol is
or
The bromide of DOPO-PN is used,
or
A bromide of Ar-DOPO-N,
or
Bromides of OD-PN.
The further preferred technical scheme is as follows: the phosphorus-bromine-containing bisphenol and the phosphorus-bromine-containing polyphenol are prepared from corresponding common bisphenol and common polyphenol through bromine bromination reaction, the dosage of the peroxide free radical initiator accounts for 20-100mol% of the phenol, the lower limit of the temperature of the chain redistribution reaction of the polyarylether is the temperature when the half-life period of the peroxide free radical initiator is 10h, and the upper limit is the boiling point of the solvent of the homogeneous organic solution.
The further preferred technical scheme is as follows: the modified resin is any one or mixture of a polyarylether or polyolefin modified by an end group, and the end group is any one of amino, sulfydryl, carboxylic acid, anhydride or cyanate.
In the invention, the modified resin accounts for 5-30wt% of the flame-retardant polyarylether-based composition.
In the invention, the main curing agent is one or a mixture of more of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring structure epoxy resin, biphenyl epoxy resin, heterocyclic epoxy resin, phenolic epoxy resin, organosilicon epoxy resin, polyfunctional group, aliphatic epoxy resin and cyanate ester modified epoxy resin, and the main curing agent accounts for 15-68wt% of the flame-retardant polyarylether-based composition.
In the invention, the secondary curing agent is one or a mixture of more of active polyester, dihydric alcohol, polyhydric alcohol, diamine, polyamine, dithiol, polythiol, dihydric phenol, polyphenol, phenolic resin, cyanate ester resin, anhydride, dicyandiamide and benzoxazine, and the secondary curing agent accounts for 0.1-12wt% of the flame-retardant polyarylether-based composition.
In the invention, the curing accelerator is one or a mixture of more of tertiary amine compounds, imidazole compounds, phosphine compounds, substituted urea compounds, phenolic compounds and boron trifluoride amine complexes, and accounts for 0.02-5.0wt% of the main curing agent.
In the invention, the filler is SiO2、Al2O3、TiO2、ZnO、MgO、Bi2O3、AlN、Si3N4、SiC、BN、Al(OH)3、Mg(OH)2、BaTiO3、SrTiO3、Mg2TiO4、Bi2(TiO3)3、PbTiO3、NiTiO3、CaTiO3、ZnTiO3、Zn2TiO4、BaSnO3、Bi2(SnO3)3、CaSnO3、PbSnO3、MgSnO3、SrSnO3、ZnSnO3、BaZrO3、CaZrO3、PbZrO3、MgZrO3、SrZrO3、ZnZrO3The flame-retardant polyarylether composite material comprises one or more of graphite oxide, graphite fluoride, talcum powder, mica powder, kaolin, solid glass microspheres, hollow glass microspheres, glass fibers, basalt fibers and carbon fibers, and also can comprise one or more of polytetrafluoroethylene pre-sintered materials, ultrahigh molecular weight polyethylene fibers, Kevlar fibers, polyimide, polyetherimide, polyetheretherketone and polyphenylene sulfide, wherein the amount of the filler accounts for 1-80wt% of the flame-retardant polyarylether composite material.
The further preferred technical scheme is as follows: the flame retardant is one or a mixture of more of an aluminum magnesium flame retardant, a boron zinc flame retardant, a molybdenum tin flame retardant, a bromine flame retardant, antimony trioxide, a phosphorus flame retardant and a nitrogen flame retardant, and the amount of the flame retardant accounts for 1-10wt% of the flame-retardant polyarylether-based composition.
A prepreg prepared by adopting a flame-retardant polyarylether-based composition comprises the following specific steps: preparing a uniform dispersion liquid of the flame-retardant polyarylether-based composition with the solid content of 35-75wt/v%, impregnating fiber cloth with the uniform dispersion liquid, and baking and drying to obtain a prepreg.
The fiber cloth is any one of electronic grade alkali-free glass fiber cloth, carbon fiber, boron fiber, Kevlar, polyimide, polytetrafluoroethylene, polyester and LCP.
The baking and drying are divided into two stages, the baking and drying temperature of the first stage is 30-110 ℃, and the baking and drying temperature of the second stage is 110-180 ℃.
A thermosetting copper-clad plate manufactured by prepregs comprises the following specific steps: the prepreg and the copper foil covered on the surface layer are overlapped together and laminated to obtain the thermosetting copper-clad plate,wherein the number of the prepregs is more than or equal to 1, the number of the copper foils is 1 or 2, the laminating temperature is 130-250 ℃, and the laminating pressure is 40-100kg/cm2The laminating time is 5-480 min.
The invention has the following advantages: firstly, taking a double-end hydroxyl type common polyarylether oligomer and a multi-end hydroxyl type common polyarylether oligomer as main resin, and matching with modified resin, a main curing agent, a secondary curing agent, a curing accelerator, a filler and a flame retardant, the prepared prepreg has the advantages of uniform gel content, strong resin adhesive force, smooth surface, proper toughness and viscosity and prominent flame retardant property, and meets various performance requirements of the current high-frequency and high-speed communication field on the copper-clad plate material; secondly, adding double-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer and multi-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer into the main resin, so that the prepared prepreg can ensure enough flame retardant performance with relatively less flame retardant even without flame retardant; thirdly, the hydroxyl-terminated polyarylether oligomer, the flame-retardant polyarylether base composition, the prepreg and the final copper-clad plate have the advantages of simple and efficient production method.
Drawings
FIG. 1 is Table 1 showing the formulations of examples 1-4 recorded in the present invention.
FIG. 2 is Table 1, continuation 1, in which the formulations of examples 1-4 are recorded in the present invention.
FIG. 3 is a table 1, continuation 2 of the invention recording the formulations of examples 1-4.
Fig. 4 is a table 2 in which the test performance results of the prepregs and the copper-clad plates of examples 1 to 4 are recorded in the present invention.
Detailed Description
The following description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention.
Synthesis example 1
450 parts of polyphenylene oxide (Mn = 23000) was dissolved in toluene to prepare a 20wt/v% solution, and then 5 parts of 4, 4' -biphenol, 20 parts of 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane, 20 parts of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide and 55 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide were added, and after stirring and mixing them well, 50 parts of dibenzoyl peroxide was gradually added in portions, and the reaction was carried out for 8 hours while controlling the system temperature at 100 ℃.
Then, adding a small amount of methanol into the system, slowly stirring and uniformly mixing, standing overnight at room temperature, and filtering to remove high molecular weight polyphenylene ether chains which cannot fully perform chain redistribution reaction; next, a large amount of methanol was added to the filtrate, vigorously stirred to sufficiently precipitate a hydroxyl terminated polyphenylene ether oligomer, and similarly subjected to filtration-washing-drying, etc. to prepare a product having a number average molecular weight Mn =2452 and a weight average molecular weight Mw = 4750.
Synthesis example 2
380 parts of polyphenylene ether (Mn = 19000) was dissolved in toluene to prepare a 25wt/v% solution, and then 15 parts of tetrabromobisphenol a, 10 parts of 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane, 15 parts of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide and 60 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide were added thereto, and after stirring and mixing them well, 32 parts of dibenzoyl peroxide was gradually added in portions, and the reaction was carried out for 24 hours while controlling the system temperature to 90 ℃.
Then, adding a small amount of methanol into the system, slowly stirring and uniformly mixing, standing overnight at room temperature, and filtering to remove high molecular weight polyphenylene ether chains which cannot fully perform chain redistribution reaction; next, a large amount of methanol was added to the filtrate, vigorously stirred to sufficiently precipitate a hydroxyl-terminated polyphenylene ether oligomer, and similarly subjected to filtration-washing-drying and the like to prepare a product having a number average molecular weight Mn =2635 and a weight average molecular weight Mw = 4980.
Synthesis example 3
400 parts of polyphenylene ether (Mn = 35000) was dissolved in toluene to prepare a 14.5wt/v% solution, and then 6 parts of tetrabromobisphenol A, 4 parts of 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane, 25 parts of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide and 65 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide were added, and after stirring and mixing them well, 35 parts of dibenzoyl peroxide were gradually added in steps, and the reaction was carried out for 6 hours while controlling the system temperature to 105 ℃.
Then, adding a small amount of methanol into the system, slowly stirring and uniformly mixing, standing overnight at room temperature, and filtering to remove high molecular weight polyphenylene ether chains which cannot fully perform chain redistribution reaction; next, a large amount of methanol was added to the filtrate, and vigorously stirred to sufficiently precipitate a hydroxyl-terminated polyphenylene ether oligomer, and the product was also prepared through the steps of filtration-washing-drying, etc., and had a number average molecular weight Mn =2860 and a weight average molecular weight Mw = 5386.
Synthesis example 4
180 parts of polyphenylene ether (Mn = 19000) was dissolved in toluene to prepare a 14.5wt/v% solution, and then 6 parts of tetrabromobisphenol a, 4 parts of 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane, 25 parts of 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide and 65 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide bromide were added, and after stirring and mixing them well, 35 parts of dibenzoyl peroxide were gradually added in portions, and the system temperature was controlled at 100 ℃ to react for 8 hours.
Then, adding a small amount of methanol into the system, slowly stirring and uniformly mixing, standing overnight at room temperature, and filtering to remove high molecular weight polyphenylene ether chains which cannot fully perform chain redistribution reaction; next, a large amount of methanol was added to the filtrate, vigorously stirred to sufficiently precipitate a hydroxyl-terminated polyphenylene ether oligomer, and similarly subjected to filtration-washing-drying and the like to prepare a product having a number average molecular weight Mn =1478 and a weight average molecular weight Mw = 3054.
In the 4 synthesis examples, the above-mentioned modes of sufficient stirring, slow addition, small amount, slow stirring, standing overnight, large amount and vigorous stirring are all steps performed according to the existing laboratory operation specifications, and during operation, the automatic adjustment within a reasonable range can be performed according to the actual reaction condition, so as to ensure that the final synthesis reaction is smoothly performed.
Examples 1 to 4
Uniformly dispersing matrix resin, modified resin, a main curing agent, a secondary curing agent, a curing accelerator, a filler and a flame retardant in toluene, controlling the solid content of the dispersion to be 60wt%, dipping 1080 glass fiber cloth in the uniform dispersion, and baking to obtain a prepreg. The first stage baking and drying temperature is 60-100 ℃; the second stage baking and drying temperature is 100-170 ℃. And (3) superposing 8 prepregs, respectively attaching loz copper foils to two surfaces of each prepreg, and laminating for several hours under vacuum, pressure and high temperature to obtain the copper-clad plate, wherein the specific formula is shown in table 1 in the attached figure 1, table 1 continuation 1 in the attached figure 2 and table 1 continuation 2 in the attached figure 3.
Wherein, the test performances of the prepreg and the copper-clad plate are detailed in a table 2 in an attached figure 4.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various modifications can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. These are non-inventive modifications, which are intended to be protected by patent laws within the scope of the claims appended hereto.
Claims (10)
1. The flame-retardant polyarylether-based composition comprises main resin and is characterized in that: the main resin comprises any one or both of double-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer and multi-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer.
2. The flame retardant polyarylether-based composition according to claim 1, wherein: the double-end hydroxyl type phosphorus-bromine-containing polyarylether oligomer has the structure
The structure of the multi-hydroxyl type phosphorus bromine-containing polyarylether oligomer is
Or
Or
Or
Wherein T is hydroxy, L1Is structured as
R1-R4Each independently represents a C1-C12 hydrocarbon chain or aryl group.
3. The flame retardant polyarylether-based composition according to claim 1, wherein: the main resin also comprises any one or both of a double-end hydroxyl type common polyarylether oligomer and a multi-end hydroxyl type common polyarylether oligomer.
4. The flame retardant polyarylether-based composition according to claim 3, wherein: the structure of the double-end hydroxyl type common polyarylether oligomer is
Or
The structure of the multi-end hydroxyl type common polyarylether oligomer is
Or
Or
Wherein R is1-R4Each independently represents a C1-C12 hydrocarbon chain or aryl group, R5-R12、R14-R21、R23-R34、R37-R44And R47-R62Each independently represents H, C1-C12 carbon hydrocarbon chain, aryl or halogen, R22、R45And R46Each independently represents H or a C1-C12 hydrocarbon chain, R13、R35And R36Each independently represents any one of the following functional groups
Wherein R is63-R68Each independently represents a C1-C12 hydrocarbon chain or an aryl group.
5. The flame retardant polyarylether-based composition according to claim 3, wherein: the main resin comprises double-hydroxyl-group type phosphorus-bromine-containing polyarylether oligomers, multi-hydroxyl-group type phosphorus-bromine-containing polyarylether oligomers, double-hydroxyl-group type common polyarylether oligomers and multi-hydroxyl-group type common polyarylether oligomers, wherein the double-hydroxyl-group type common polyarylether oligomers and the multi-hydroxyl-group type common polyarylether oligomers account for 50-99wt% of the total amount of the four hydroxyl-group-containing polyarylether oligomers; the ratio of the double-hydroxyl-terminated type phosphorus-bromine-containing polyarylether oligomer to the multi-hydroxyl-terminated type phosphorus-bromine-containing polyarylether oligomer is 2:8-7: 3; the ratio of the bi-hydroxyl-terminated common polyarylether oligomer to the multi-hydroxyl-terminated common polyarylether oligomer is 1:9-8: 2.
6. The flame retardant polyarylether composition according to claim 5, wherein the preparation method of the hydroxyl terminated polyarylether oligomer sequentially comprises the following steps:
s1, adding phenol into the homogeneous organic solution of the polyarylether, stirring and mixing, adding the peroxide radical initiator in batches, continuously stirring for 6-72 hours, and finally performing redistribution reaction on the chains of the polyarylether to obtain a primary system;
s2, adding a poor solvent of polyarylether into the initial system for the first time, stirring to separate out high molecular weight polyarylether which cannot undergo chain redistribution reaction, filtering to remove the precipitate, adding more poor solvent of polyarylether into the filtrate than the amount of polyarylether added for the first time, continuously stirring and mixing to separate out oligomer, and finally filtering, washing and drying in sequence to obtain the hydroxyl-terminated polyarylether oligomer.
7. The flame retardant polyarylether-based composition according to claim 6, wherein: the number average molecular weight of the polyarylether is 8000-50000, and the structure is
The solvent of the homogeneous organic solution is any one or a mixture of toluene, xylene and N, N-dimethylformamide; the phenol consists of four types of common bisphenol, common polyphenol, phosphorus bromine-containing bisphenol and phosphorus bromine-containing polyphenol; the peroxide free radical initiator is any one or a mixture of two of dibenzoyl peroxide or tert-butyl peroxybenzoate; the poor solvent is any one or a mixture of more of methanol, ethanol, isopropanol, butanol, ether or ester, and the common bisphenol has a structure of
The common polyphenol has the structure of
The structure of the phosphorus bromine-containing bisphenol is
The structure of the phosphorus and bromine containing polyphenol is
8. The flame retardant polyarylether-based composition according to claim 7, wherein: the phosphorus-bromine-containing bisphenol and the phosphorus-bromine-containing polyphenol are prepared from corresponding common bisphenol and common polyphenol through bromine bromination reaction, the dosage of the peroxide free radical initiator accounts for 20-100mol% of the phenol, the lower limit of the temperature of the chain redistribution reaction of the polyarylether is the temperature when the half-life period of the peroxide free radical initiator is 10h, and the upper limit is the boiling point of the solvent of the homogeneous organic solution.
9. The flame retardant polyarylether-based composition according to claim 1, wherein: the modified resin is any one or mixture of a polyarylether or polyolefin modified by an end group, and the end group is any one of amino, sulfydryl, carboxylic acid, anhydride or cyanate.
10. The flame retardant polyarylether-based composition according to claim 9, wherein: the flame retardant is one or a mixture of more of an aluminum magnesium flame retardant, a boron zinc flame retardant, a molybdenum tin flame retardant, a bromine flame retardant, antimony trioxide, a phosphorus flame retardant and a nitrogen flame retardant, and the amount of the flame retardant accounts for 1-10wt% of the flame-retardant polyarylether-based composition.
Priority Applications (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
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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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| US20020077447A1 (en) * | 2000-12-19 | 2002-06-20 | Industrial Technology Research Institute | Curable polyphenylene ether resin, composition made therefrom, and process for preparing the resin |
| JP2006089683A (en) * | 2004-09-27 | 2006-04-06 | Nippon Steel Chem Co Ltd | Flame retardant resin composition |
| CN109988298A (en) * | 2017-12-29 | 2019-07-09 | 广东生益科技股份有限公司 | A kind of modified polyphenylene ether resin, compositions of thermosetting resin and application thereof |
| US20190300649A1 (en) * | 2016-12-28 | 2019-10-03 | Shengyi Technology Co., Ltd. | Flame-retardant polyphenylene ether resin composition |
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| US20020077447A1 (en) * | 2000-12-19 | 2002-06-20 | Industrial Technology Research Institute | Curable polyphenylene ether resin, composition made therefrom, and process for preparing the resin |
| JP2006089683A (en) * | 2004-09-27 | 2006-04-06 | Nippon Steel Chem Co Ltd | Flame retardant resin composition |
| US20190300649A1 (en) * | 2016-12-28 | 2019-10-03 | Shengyi Technology Co., Ltd. | Flame-retardant polyphenylene ether resin composition |
| CN109988298A (en) * | 2017-12-29 | 2019-07-09 | 广东生益科技股份有限公司 | A kind of modified polyphenylene ether resin, compositions of thermosetting resin and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN114516956B (en) * | 2021-12-17 | 2023-09-05 | 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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