CN108341947B - Intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide and preparation method thereof - Google Patents
Intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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
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- 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 an intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide and a preparation method thereof, wherein a phosphorus/silicon-containing diphenol monomer or a silicon-containing difluorodiamide or a phosphorus-containing difluorodiamide monomer is used for preparing the flame-retardant semi-aromatic copolymerized aryl ether amide through solution polycondensation, the intrinsic viscosity [ eta ] of the semi-aromatic copolymerized aryl ether amide is 0.65-1.01 dL/g, the vertical combustion level is V-2-V-0 level, the limiting oxygen index is 26.8-45.5%, and the tensile strength is 65-108 MPa. The intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide disclosed by the invention has the characteristics of halogen-free flame retardance, no molten drop, easiness in processing, high mechanical strength and the like, and has wider application as engineering plastics.
Description
Technical Field
The invention belongs to the technical field of synthetic flame-retardant high polymer materials. The invention relates to a copolymerized aryl ether amide containing phosphorus and silicon elements and a preparation method thereof.
Background
The semi-aromatic polyamide has excellent mechanical property and chemical resistance, is widely applied to daily life of people, and is particularly applied to industries such as electronic appliances, automobile manufacturing, aerospace and the like. However, semi-aromatic polyamides have a narrow processing window and are flammable, which limits their use to some extent.
The semi-aromatic polyaryletheramide serving as a high-performance plastic not only has excellent mechanical properties and thermal properties of polyarylethers and semi-aromatic polyamide, but also improves the toughness and processing flowability of polyarylethers, and overcomes the defect of narrow processing window of semi-aromatic polyamide. In addition, the semi-aromatic polyaryletheramide has the advantages of high yield, high molecular weight, easiness in processing, high temperature resistance, corrosion resistance and the like (CN 103739839A). However, the semi-aromatic polyaryletheramides are flammable, which limits their use to some extent. In recent years, the research on the flame retardant modification of polyamide is also reported, but most of the research is to realize the flame retardant by adding a flame retardant. For example, halogen-free flame retardant polyamide (CN201380045938.9) from dupont company reports that flame retardancy of polyamide is achieved by adding halogen-free flame retardant, and this method has problems of poor compatibility of additive and substrate, migration of additive, and poor flame retardant durability.
Disclosure of Invention
The invention aims to provide an intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide and a preparation method thereof aiming at the defects of the prior art, and is characterized in that a flame-retardant monomer is copolymerized with aromatic diphenol and semi-aromatic difluorodiamide to prepare the semi-aromatic copolymerized aryl ether amide, so that the semi-aromatic copolymerized aryl ether amide has the advantages of excellent flame-retardant property, high temperature resistance, good mechanical property and the like, and is widely applied.
The invention provides an intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide, which has a main molecular structure general formula as follows:
wherein: m and n are mole percentages, and m + n is 100;
any one of them.
Further, when n in the formula I is 5-30 mol%, namely Ar2The mol percentage content of the aromatic polyether amide is 2.5-15 mol%, and the prepared semi-aromatic copolymerized aromatic ether amide has the characteristic viscosity number [ eta ] of]0.69-1.01dL/g, the limiting oxygen index is 30.0-45.5%, the UL-94 vertical combustion grade is V-2-V-0 grade, and the tensile strength is 68-108 MPa;
when n in the formula II is 5-30 mol%, namely R2The molar percentage of the component (a) is 2.5-15 mol%Intrinsic viscosity [ eta ] of the semi-aromatic copolymerized aryl ether amide]0.65-0.98dL/g, limit oxygen index of 26.8-38.5%, UL-94 vertical burning grade of stepless V-2-V-0 grade, and tensile strength of 65-105 MPa.
Further, the structure Ar1Any one of the diphenols from:
structure Ar2Any one of the diphenols from:
structure R1 is derived from any one of the following semi-aromatic difluorodiamides:
structure R2 is derived from any one of the following difluorodiamides:
the method for preparing the intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide provided by the invention specifically comprises the following steps:
(1) when the intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide as shown in the formula one is prepared, the method comprises the following steps:
in a reaction vessel, adding the obtained Ar1Any one of diphenol DHTPM, FDP or PEBP, Ar obtained by the above2Any one of diphenol DOPO-HQ, 2DOPO-DMSi or 2DOPO-DPSi, the obtained R1Under the protection of inert gas, the semi-aromatic difluorodiamide BFBB or BFBH or BFBO or BFBD any one, catalyst, dehydrating agent and high boiling point solvent are heated and kept at a certain temperature for reaction to obtain the productPurifying the solution containing the copolymer as shown in the formula I to obtain the intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide as shown in the formula I;
(2) when the intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide as shown in the formula II is prepared, the method comprises the following steps:
in a reaction vessel, adding the obtained Ar1Any one of diphenols DHTPM, FDP or PEBP, said R2Any one of the difluorodiamide BFBPSi or BFPPO, the obtained R1Under the protection of inert gas, heating and keeping a certain temperature for reaction to obtain liquid containing the copolymer as shown in the formula II, and purifying to obtain the intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide as shown in the formula II.
Further, the reaction conditions in the above reaction are: the temperature is controlled at 150-190 ℃ for dehydration reaction for 1-6h, and the reaction is continued at 190-220 ℃ for 6-12 h.
Further, said obtained Ar added in the preparation method2The molar percentage of any diphenol in the total reaction raw materials is 2.5-15 mol%, and the R is obtained by adding2The molar percentage of any one of the difluorodiamides in the total reaction raw materials is 2.5-15 mol%.
Further, the catalyst in the preparation method is one of sodium carbonate, potassium carbonate and cesium carbonate; the dehydrating agent is one of methylbenzene, ethylbenzene, o-xylene, m-xylene and p-xylene; the inert gas is one of nitrogen and argon; the high boiling point solvent is one of formamide, acetamide, N-methyl pyrrolidone and sulfolane.
Further, the purification steps in the preparation method specifically include: and (2) controlling the temperature of the reaction liquid to be 80-150 ℃, pouring the reaction liquid into deionized water, precipitating filamentous polymers, repeatedly washing with water and ethanol, drying, crushing the polymers by using a crusher, washing with water and ethanol again, and drying in vacuum to obtain the semi-aromatic copolymerized aryl ether amide.
Further, the preparation method described above gives Ar2The phosphorus/silicon-containing diphenol 2DOPO-DMSi or 2DOPO-DPSi is prepared by the following steps: dissolving 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) in an organic solvent in a reaction vessel, and dropwise adding a dichlorosilane solution while keeping a certain temperature; an acid-binding agent is also required to be added, and the acid-binding agent can be triethylamine; after the dichlorosilane is dripped, keeping the dichlorosilane at a certain temperature for reaction to generate reaction liquid containing the phosphorus/silicon-containing diphenol, and purifying to obtain the phosphorus/silicon-containing diphenol;
further, in the above preparation method, the dichlorosilane solution is added dropwise while controlling the temperature at 5 to 25 ℃, the amount of the added dropwise is DOPO-HQ: dichlorosilane 2-2.5; the triethylamine can be dissolved in the organic solvent before the dichlorosilane solution is dripped, or can be added after the dripping, or is dripped together with the dichlorosilane solution; after the dichlorosilane is dripped, the temperature is controlled to be 25-60 ℃ and the reaction lasts for 10-24 h.
The organic solvent is at least one of formamide, dimethylformamide and dimethylacetamide.
The purification steps in the preparation method are as follows: and precipitating the reaction solution at low temperature by using ethanol, then recrystallizing by using a recrystallization solvent, and drying in vacuum to obtain the phosphorus/silicon diphenol.
The recrystallization solvent is at least one of methanol, ethanol, isopropanol and tetrahydrofuran.
Further, the silicon-or phosphorus-containing difluorodiamide BFBPSi or BFPPO to obtain R2 described in the preparation method is prepared by the following steps: dissolving silicon-containing diamine or phosphorus-containing diamine and triethylamine as acid-binding agents in dichloromethane at room temperature; adding dichloromethane into a reaction container, dissolving p-fluorobenzoyl chloride into dichloromethane, adding the prepared silicon-containing diamine or phosphorus-containing diamine solution, continuing to react for a period of time at room temperature after the diamine solution is dropwise added, generating a reaction liquid containing the silicon-containing or phosphorus-containing difluorodiamide, and purifying to obtain the silicon-containing or phosphorus-containing difluorodiamide.
Further, in the above preparation method, after the diamine solution is added dropwise, the reaction is continued at room temperature for 8 hours.
The purification steps in the preparation method are as follows: and (3) carrying out suction filtration on the reaction liquid to remove triethylamine hydrochloride, collecting filtrate, carrying out rotary evaporation to remove the solvent, collecting solid, washing with deionized water, recrystallizing with ethanol, and carrying out vacuum drying to obtain the silicon-containing or phosphorus-containing difluorodiamide.
The invention has the following advantages:
1. the synthesis of the flame-retardant monomer provided by the invention has the advantages of simple preparation process, mild reaction conditions, high product yield, low pollution, easy solvent recovery and the like.
2. The invention adopts one-pot solution polycondensation for copolymerization to prepare the intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide, and the polymer has simple synthesis, is halogen-free flame retardant and belongs to an environment-friendly material.
3. According to the invention, the flame-retardant monomer is introduced into the polymer, and the semi-aromatic copolymerized aromatic ether amide can achieve good flame-retardant and anti-dripping effects only by introducing the flame-retardant monomer with a lower proportion (less than or equal to 15 mol%), which is mainly the introduction of the silicon-containing flame-retardant monomer, so that the material is easier to form carbon during combustion, the stability of a carbon layer is enhanced, the condensed phase flame-retardant effect is realized, and meanwhile, the introduction of the phosphorus element is combined with the silicon element, so that the synergistic flame-retardant effect is achieved.
4. The intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide provided by the invention has the advantages of excellent flame retardance, easiness in processing, high temperature resistance and the like, and simultaneously maintains the excellent mechanical property of the polymer, mainly due to the existence of the side group of the benzene ring in the copolymer, so that the polymer molecular chains have pi-pi conjugation, and the mechanical property of the material is well maintained.
5. The intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide provided by the invention can be used for preparing heat-resistant and chemical corrosion-resistant parts and products, can also be prepared into special fibers and films, and can also be blended with other macromolecular polymers for use, so that the mechanical property of the material is improved, and the flame-retardant and anti-dripping characteristics of the material can be endowed, and therefore, the intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide has wide application prospects.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of BFBPSi prepared in example 37 of this invention, wherein 0.1ppm is the chemical shift of the hydrogen of the methyl group on the siloxane, 1.3ppm, 1.6ppm, 3.2ppm are the chemical shifts of the hydrogen of the three methylene groups, respectively, 6.8ppm is the chemical shift of the hydrogen on the amide, and 7.0ppm and 7.7ppm are the chemical shifts of the hydrogen on the benzene ring, indicating the successful synthesis of the silicon-containing difluorodiamide BFBPSi.
FIG. 2 is the NMR spectrum of BFBPSi-containing bisphenol fluorene copolymerized aryl ether adipamide prepared in example 43 of the present invention, and it can be seen from the chart that 0.1ppm is the hydrogen chemical shift of methyl group on siloxane, which indicates the successful introduction of the flame retardant monomer BFBPSi into the copolymer.
FIG. 3 is a digital photograph of a UL-94 vertical burning test and a limited oxygen index test of a sample containing BFBPSi bisphenol fluorene copolymerized aryl ether adipamide prepared in example 43 of the present invention, and it can be seen from the photograph that the copolymer has a certain char-forming flame retardant effect.
FIG. 4 is a graph showing tensile strength curves of the copolymers prepared in comparative example 2, example 42 and example 43 of the present invention, and it can be seen that the copolymers have good mechanical properties.
Detailed Description
The following examples are given to further illustrate the invention. It should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that the skilled person in this field could make modifications and variations of the present invention without departing from the spirit or essential attributes thereof.
In addition, it is worth mentioning that: 1) intrinsic viscosity [. eta. ] of inherently flame retardant semi-aromatic copolyarylamides obtained in the following examples]The preparation method comprises the following steps of (1) preparing a solution with the concentration of 0.5g/dL by using N-methyl pyrrolidone (NMP) as a solvent, and testing the solution at 25 ℃ by using an Ubbelohde viscometer; 2) the limiting oxygen index of the tested product is 120 multiplied by 6.5 multiplied by 3.2mm3According to ASTM D2863-97, on an HC-2 oxygen index apparatusDetermining; 3) the vertical burning is carried out to make the thickness of the material 120X 13.0X 3.2mm3According to UL-94 standard, measured with a model CZF-2 vertical burner; 4) the tensile properties of the samples were tested using a universal material tensile tester, model Instron 3366, Instron, USA, according to the GB/T1040.2-2006 (ISO 527-2: 1993).
Example 1
Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (212g, 2mol) sodium carbonate, 200ml toluene, (332.5g, 0.95mol)9, 9-bis (4-hydroxyphenyl) fluorene (also known as bisphenol fluorene, FDP), (16.2g, 0.05mol) DOPO-HQ and 1500ml formamide into a reaction container, dehydrating at 175 ℃ for 3h under the protection of nitrogen, and reacting at 200 ℃ for 8h to obtain a viscous copolymer solution; then purifying the copolymer solution, which comprises the following steps: cooling the solution to 120 ℃, pouring the solution into water while stirring, and separating out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 80 ℃ for l0h to obtain the purified bisphenol fluorene copolymerized aryl ether succinamide containing DOPO-HQ.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.83 dL/g; the limiting oxygen index is 31.5%; the vertical burning grade is V-1, and the tensile strength is 85 MPa.
Examples 2 to 4
The raw material ratio of the bisphenol fluorene copolymerized aryl ether succinamide prepared in the example 1 is adjusted to prepare the bisphenol fluorene copolymerized aryl ether succinamide with different DOPO-HQ contents, and the specific data are shown in Table 1.
TABLE 1
Example 5
Adding (360g, 1mol) bis (4-fluorobenzoyl) hexamethylenediamine (BFBH), (276g, 2mol) potassium carbonate, 200ml p-xylene, (334.5g, 0.95mol)4,4' -diphenylmethylene bisphenol (also known as bisphenol BP, DHTPM), (16.2g, 0.05mol) DOPO-HQ and 1500ml sulfolane into a reaction container, then dehydrating and reacting for 1h at 190 ℃ under the protection of nitrogen, then reacting for 12h at 200 ℃ to obtain a viscous copolymer solution, cooling the solution to 80 ℃, pouring the solution into water while stirring to separate out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 80 ℃ for l0h to obtain the purified bisphenol BP copolymerized aromatic ether adipamide containing DOPO-HQ.
The intrinsic viscosity [ eta ] of the copolymerized polyarylether adipamide is 0.82 dL/g; the limiting oxygen index is 30.5%; the vertical burning rate is V-2, and the tensile strength is 82 MPa.
Examples 6 to 8
The raw material ratio of the bisphenol BP copolymerized aromatic ether adipamide prepared in the example 5 is adjusted to prepare the bisphenol BP copolymerized aromatic ether adipamide with different DOPO-HQ contents, and the specific data are shown in the table 2.
TABLE 2
Example 9
Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene, (275.5g, 0.95mol)4,4' - (1-phenylethyl) bisphenol (also known as bisphenol AP, PEBP), (16.2g, 0.05mol) DOPO-HQ and 1500ml sulfolane into a reaction container, dehydrating at the temperature of 150 ℃ for 6 hours under the protection of nitrogen, reacting at the temperature of 220 ℃ for 6 hours to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring the solution into water while stirring to separate out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 80 ℃ for l0h to obtain the purified bisphenol AP copolymerized aryl ether succinamide containing DOPO-HQ.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.85 dL/g; the limiting oxygen index is 30.0%; the vertical burning grade is V-1, and the tensile strength is 95 MPa.
Examples 10 to 12
The raw material ratio of the bisphenol AP copolymerized aryl ether succinamide prepared in the example 9 is adjusted to prepare the bisphenol AP copolymerized aryl ether succinamide with different DOPO-HQ contents, and the specific data are shown in Table 3.
TABLE 3
Example 13
(1) Preparation of 2 DOPO-DMSi: 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) (101g, 1mol) triethylamine (356.4g, 1.1mol) and 2000ml dimethylacetamide were added to a reaction vessel under nitrogen protection at 5 ℃ with mechanical stirring. Then, the prepared solution [ (64.5g, 0.5mol) dichlorodimethylsilane, 500ml dimethylacetamide ] was added dropwise at 1 drop per second; after the dropwise addition, controlling the temperature at 40 ℃ and reacting for 24 hours to obtain clear and transparent liquid; and (3) precipitating the reaction solution at low temperature by using ethanol, recrystallizing the ethanol, and drying in vacuum to obtain the 2 DOPO-DMSi.
(2) Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (212g, 2mol) sodium carbonate, 200ml toluene, (332.5g, 0.95mol)9, 9-bis (4-hydroxyphenyl) fluorene (also known as bisphenol fluorene, FDP), (35.2g, 0.05mol)2DOPO-DMSi and 1500ml azomethyl pyrrolidone into a reaction vessel, then carrying out dehydration reaction at the temperature of 170 ℃ for 3h under the protection of nitrogen, then carrying out reaction at the temperature of 200 ℃ for 8h to obtain a viscous copolymer solution, cooling the solution to 150 ℃, pouring the solution into water while stirring, and separating out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 80 ℃ for l0h to obtain the purified bisphenol fluorene copolymerized aryl ether succinamide containing 2 DOPO-DMSi.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.82 dL/g; the limiting oxygen index is 33.5%; the vertical burning rating is V-1 and the tensile strength is 88 MPa.
Examples 14 to 16
The bisphenol fluorene copolymerized aryl ether succinamide prepared in example 13 was prepared by adjusting the raw material ratio, and the specific data are shown in table 4.
TABLE 4
Example 17
Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (212g, 2mol) sodium carbonate, 200ml ethylbenzene, (334.5g, 0.95mol)4,4' -diphenylmethylene bisphenol (also known as bisphenol BP, DHTPM), (35.2g, 0.05mol)2DOPO-DMSi and 1500ml sulfolane into a reaction container, then dehydrating at the temperature of 170 ℃ for 4h under the protection of nitrogen, then reacting at the temperature of 220 ℃ for 6h to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring the solution into water while stirring, and separating out a gray fine strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the purified bisphenol BP copolymerized aromatic ether succinamide containing 2 DOPO-DMSi.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.85 dL/g; the limiting oxygen index is 32.3%; the vertical burning rate is V-2, and the tensile strength is 79 MPa.
Examples 18 to 20
The raw material ratio of the bisphenol BP copolymerized aryl ether succinamide prepared in the example 17 is adjusted to prepare the bisphenol BP copolymerized aryl ether succinamide with different 2DOPO-DMSi contents, and the specific data are shown in Table 5.
TABLE 5
Example 21
Adding (360g, 1mol) bis (4-fluorobenzoyl) hexanediamine (BFBH), (276g, 2mol) potassium carbonate, 200ml toluene, (203.0g, 0.70mol)4,4' - (1-phenylethyl) bisphenol (also known as bisphenol AP, PEBP), (35.2g, 0.05mol)2DOPO-DMSi and 1500ml sulfolane into a reaction vessel, then carrying out dehydration reaction at 160 ℃ for 4h under the protection of nitrogen, then carrying out reaction at 190 ℃ for 12h to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring the solution into water while stirring, and separating out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 80 ℃ for l0h to obtain the purified bisphenol AP copolymerized aromatic ether adipamide containing 2 DOPO-DMSi.
The intrinsic viscosity [ eta ] of the copolymerized polyarylether adipamide is 0.85 dL/g; the limiting oxygen index is 31.2%; the vertical burning rate was V-1 and the tensile strength was 105 MPa.
Examples 22 to 24
The raw material ratio of the bisphenol AP copolymerized aryl ether adipamide prepared in the example 21 is adjusted to prepare the bisphenol AP copolymerized aryl ether adipamide with different 2DOPO-DMSi contents, and the specific data are shown in Table 6.
TABLE 6
Example 25
(1) Preparation of 2 DOPO-DPSi: 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) (101g, 1mol) triethylamine (356.4g, 1.1mol) and 2000ml dimethylacetamide were added to a reaction vessel under nitrogen protection at a temperature of about 10 ℃ with mechanical stirring. Then, the solution prepared [ (126.5g, 0.5mol) diphenyldichlorosilane, 500ml dimethylacetamide ] is added dropwise, 1 drop per second; after the dropwise addition, controlling the temperature at 60 ℃ and reacting for 12 hours to obtain clear and transparent liquid; and (3) carrying out low-temperature precipitation on the reaction liquid by using ethanol, recrystallizing by using methanol, and carrying out vacuum drying to obtain the 2 DOPO-DPSi.
(2) Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (652g, 2mol) cesium carbonate, 200ml o-xylene, (332.5g, 0.95mol)9, 9-bis (4-hydroxyphenyl) fluorene (also known as bisphenol fluorene, FDP), (41.4g, 0.05mol)2DOPO-DPSi and 1500ml azomethyl pyrrolidone into a reaction vessel, dehydrating at 185 ℃ for 2.5h under the protection of nitrogen, reacting at 200 ℃ for 8h to obtain a viscous copolymer solution, cooling the solution to 150 ℃, pouring water while stirring to separate out a gray strip-shaped polymer crude product; washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the purified bisphenol fluorene copolymerized aryl ether succinamide containing 2 DOPO-DPSi.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.80 dL/g; the limiting oxygen index is 35.5%; the vertical burning grade is V-0, and the tensile strength is 88 MPa.
Examples 26 to 28
The bisphenol fluorene copolymerized aryl ether succinamide prepared in example 25 was prepared by adjusting the raw material ratio, and the specific data are shown in table 7.
TABLE 7
Examples 29 to 32
Bisphenol fluorene copolymerized aryl ether sebacamide with different 2DOPO-DPSi contents was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in bisphenol fluorene copolymerized aryl ether succinamide prepared in example 25 with (416g, 1mol) bis (4-fluorobenzoyl) decanediamine (BFBD), and adjusting the ratio of other raw materials as shown in table 8.
TABLE 8
Example 33
Adding (360g, 1mol) bis (4-fluorobenzoyl) hexamethylenediamine (BFBH), (652g, 2mol) cesium carbonate, 200ml toluene, (275.5g, 0.95mol)4,4' - (1-phenylethyl) bisphenol (also known as bisphenol AP, PEBP), (41.4g, 0.05mol)2DOPO-DPSi and 1500ml acetamide into a reaction vessel, dehydrating at the temperature of 170 ℃ for 3 hours under the protection of nitrogen, reacting at the temperature of 200 ℃ for 8 hours to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring the solution into water while stirring, and separating out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 80 ℃ for l0h to obtain the purified bisphenol AP copolymerized aromatic ether adipamide containing 2 DOPO-DPSi.
The intrinsic viscosity [ eta ] of the copolymerized aromatic ether adipamide is 1.01 dL/g; the limiting oxygen index is 31.6%; the vertical burning rating is V-1, and the tensile strength is 108 MPa.
Examples 34 to 36
The raw material ratio of the bisphenol AP copolymerized aryl ether adipamide prepared in the example 33 is adjusted to prepare the bisphenol AP copolymerized aryl ether adipamide with different 2DOPO-DPSi contents, and the specific data are shown in Table 9.
TABLE 9
Example 37
(1) Preparing BFBPSi: adding (248.5g, 1mol)1, 3-bis (3-aminopropyl) -1,1,3, 3-tetramethyldisiloxane and (212.5g, 2.1mol) triethylamine into 750ml dichloromethane for uniform dispersion to prepare a solution; then (333g, 2.1mol) p-fluorobenzoyl chloride and 2000ml dichloromethane are added into the reaction vessel, the temperature is controlled to be about 5 ℃, and the reaction vessel is mechanically stirred and protected by nitrogen. Then, dropwise adding the prepared solution; after the dropwise addition, controlling the temperature at 15 ℃, and stopping the reaction after the reaction is carried out for 8 hours; and (3) carrying out suction filtration on the reaction system, removing triethylamine hydrochloride, collecting filtrate, carrying out rotary evaporation, removing dichloromethane, washing for 3 times, recrystallizing with ethanol, separating out crystals, and carrying out vacuum drying to obtain BFBPSi.
(2) Adding (315.4g, 0.95mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (24.6g, 0.05mol) BFBPSi, (276g, 2mol) potassium carbonate, 200ml m-xylene, (350g, 1mol)9, 9-bis (4-hydroxyphenyl) fluorene (also called bisphenol fluorene, FDP) and 1500ml acetamide into a reaction container, then dehydrating at 185 ℃ for 2h under the protection of argon, reacting at 200 ℃ for 8h to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring into water while stirring, and separating out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the bisphenol fluorene copolymerized aryl ether succinamide containing BFBPSi after purification.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.85 dL/g; the limiting oxygen index is 31.5%; the vertical burning rating is V-1 and the tensile strength is 88 MPa.
Examples 38 to 40
The bisphenol fluorene copolymerized aryl ether succinamide with different BFBPSi content was prepared by adjusting the raw material ratio in the bisphenol fluorene copolymerized aryl ether succinamide prepared in example 37, and the specific data is shown in table 10.
Examples 41 to 44
The bisphenol fluorene copolymerized aryl ether adipamide with different BFBPSi contents was prepared by replacing bis (4-fluorobenzoyl) butanediamine (BFBB) as the raw material in the bisphenol fluorene copolymerized aryl ether succinamide prepared in example 37 with bis (4-fluorobenzoyl) hexanediamine (BFBH) and adjusting the ratio of the other raw materials as shown in table 11.
TABLE 11
Examples 45 to 48
The bisphenol fluorene copolymerized aryl ether octanediamide with different BFBPSi contents was prepared by replacing bis (4-fluorobenzoyl) butanediamine (BFBB) as the raw material in the bisphenol fluorene copolymerized aryl ether butanediamide prepared in example 37 with bis (4-fluorobenzoyl) octanediamine (BFBO) and adjusting the ratio of the other raw materials as shown in table 12.
TABLE 12
Example 49
Adding (315.4g, 0.95mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (24.6g, 0.05mol) BFBPSi, (276g, 2mol) potassium carbonate, 200ml toluene, (352g, 1mol)4,4' -diphenylmethylene bisphenol (also called bisphenol BP, DHTPM) and 1500ml acetamide into a reaction vessel, dehydrating at 190 ℃ for 2h under the protection of argon, reacting at 200 ℃ for 8h to obtain a viscous copolymer solution, cooling the solution to 120 ℃, and pouring the solution into water while stirring to separate out a gray fine strip polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the bisphenol BP copolymerized aryl ether succinamide containing BFBPSi after purification.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.78 dL/g; the limiting oxygen index is 29.5%; the vertical burning grade is V-2, and the tensile strength is 80 MPa.
Examples 50 to 52
The bisphenol BP copolymerized aryl ether succinamide with different BFBPSi contents was prepared by adjusting the raw material ratio in the bisphenol BP copolymerized aryl ether succinamide prepared in example 49, and the specific data are shown in table 13.
Watch 13
Example 53
Adding (315.4g, 0.95mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (24.6g, 0.05mol) BFBPSi, (276g, 2mol) potassium carbonate, 200ml toluene, (290g, 1mol)4,4' - (1-phenylethyl) bisphenol (also known as bisphenol AP, PEBP) and 1500ml acetamide into a reaction container, dehydrating at the temperature of 170 ℃ for 3 hours under the protection of argon, reacting at the temperature of 200 ℃ for 8 hours to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring the solution into water while stirring, and separating out a white thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the purified bisphenol AP copolymerized aryl ether succinamide containing BFBPSi.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.83 dL/g; the limiting oxygen index is 28.0%; the vertical burning rate was V-2 and the tensile strength was 94 MPa.
Examples 54 to 56
The bisphenol AP copolymerized aryl ether succinamides with different BFBPSi contents were prepared by adjusting the raw material ratios in the bisphenol AP copolymerized aryl ether succinamides prepared in example 53, and the specific data are shown in table 14.
TABLE 14
Example 57
(1) Preparing BFPPO: adding (308g, 1mol) bis (3-aminophenyl) phenylphosphine oxide (212.5g, 2.1mol) triethylamine into 750ml dichloromethane for uniform dispersion to prepare a solution; then (333g, 2.1mol) p-fluorobenzoyl chloride and 2000ml dichloromethane are added into the reaction vessel, the temperature is controlled to be about 5 ℃, and the reaction vessel is mechanically stirred and protected by nitrogen. Then, dropwise adding the prepared solution; after the dropwise addition, controlling the temperature at 15 ℃, and stopping the reaction after the reaction is carried out for 8 hours; and (3) carrying out suction filtration on the reaction system, removing triethylamine hydrochloride, collecting filtrate, carrying out rotary evaporation, removing dichloromethane, washing for 3 times, recrystallizing with ethanol, separating out crystals, and carrying out vacuum drying to obtain BFPPO.
(2) Adding (315.4g, 0.95mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (27.6g, 0.05mol) BFPPO, (276g, 2mol) potassium carbonate, 200ml toluene, (350g, 1mol)9, 9-bis (4-hydroxyphenyl) fluorene (also called bisphenol fluorene, FDP) and 1500ml formamide into a reaction container, dehydrating at 185 ℃ for 2h under the protection of nitrogen, reacting at 200 ℃ for 8h to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring into water while stirring, and separating out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the bisphenol fluorene copolymerized aryl ether succinamide containing BFPPO after purification.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.80 dL/g; the limiting oxygen index is 30.5%; the vertical burning rating is V-1 and the tensile strength is 88 MPa.
Examples 58 to 60
The bisphenol fluorene copolymerized aryl ether succinamide with different BFPPO contents was prepared by adjusting the raw material ratio in the bisphenol fluorene copolymerized aryl ether succinamide prepared in example 57, and the specific data is shown in table 15.
Watch 15
Example 61
Adding (395.2g, 0.95mol) bis (4-fluorobenzoyl) decamethylenediamine (BFBD), (27.6g, 0.05mol) BFPPO, (276g, 2mol) potassium carbonate, 200ml toluene, (352g, 1mol)4,4' -diphenylmethylene bisphenol (also called bisphenol BP, DHTPM) and 1500ml formamide into a reaction vessel, then dehydrating and reacting for 3h at 185 ℃ under the protection of nitrogen, then reacting for 8h at 200 ℃ to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring water while stirring to separate out a gray strip-shaped polymer crude product; and (2) washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the purified bisphenol BP copolymerized aryl ether sebacamide containing BFPPO.
The intrinsic viscosity [ eta ] of the copolymerized aryl ether sebacamide is 0.75 dL/g; the limiting oxygen index is 26.5%; the vertical burning grade is V-2, and the tensile strength is 76 MPa.
Examples 62 to 64
The raw material ratio of the bisphenol BP polyarylether sebacamide prepared in example 61 was adjusted to prepare bisphenol BP polyarylether sebacamide with different BFPPO contents, and the specific data are shown in table 16.
TABLE 16
Example 65
Adding (315.4g, 0.95mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (27.6g, 0.05mol) BFPPO, (276g, 2mol) potassium carbonate, 200ml toluene, (290g, 1mol)4,4' - (1-phenethyl) bisphenol (also known as bisphenol AP, PEBP) and 1500ml formamide into a reaction container, dehydrating at 175 ℃ for 2.5h under the protection of nitrogen, reacting at 200 ℃ for 8h to obtain a viscous copolymer solution, cooling the solution to 120 ℃, pouring into water while stirring, and separating out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the bisphenol AP copolymerized polyarylether succinamide containing BFPPO after purification.
The copolymer aromatic ether succinamide has the characteristic viscosity number [ eta ] of 0.82 dL/g; the limiting oxygen index is 29.5%; the vertical burning grade is V-1, and the tensile strength is 92 MPa.
Examples 66 to 68
The raw material ratio of the bisphenol AP copolymerized aryl ether sebacamide prepared in the example 65 was adjusted to prepare bisphenol AP copolymerized aryl ether sebacamide with different BFPPO contents, and the specific data are shown in Table 17.
TABLE 17
Examples 69 to 72
The bisphenol AP copolymerized aromatic ether adipamide with different BFPPO contents was prepared by replacing bis (4-fluorobenzoyl) butanediamine (BFBB) as the raw material in the bisphenol AP copolymerized aromatic ether butanediamide prepared in example 65 with bis (4-fluorobenzoyl) hexanediamine (BFBH) and adjusting the ratio of the other raw materials as shown in table 18.
Comparative example 1
Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene, (350g, 1mol)9, 9-bis (4-hydroxyphenyl) fluorene (also called bisphenol fluorene, FDP) and 1500ml formamide into a reaction container, then dehydrating at 185 ℃ for 2h under the protection of nitrogen, and reacting at 200 ℃ for 8h to obtain a viscous polymer solution, cooling the solution to 120 ℃, and pouring into water while stirring to separate out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying for 8h at 80 ℃, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the purified bisphenol fluorene polyarylether succinamide. The data are shown in Table 19.
Comparative example 2
Bisphenol fluorene polyarylether adipamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in bisphenol fluorene polyarylether succinamide prepared in comparative example 1 with (360g, 1mol) bis (4-fluorobenzoyl) hexanediamine (BFBH). The data are shown in Table 19.
Comparative example 3
Bisphenol fluorene polyarylether octanediamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in bisphenol fluorene polyarylether succinamide prepared in comparative example 1 with (388g, 1mol) bis (4-fluorobenzoyl) octanediamine (BFBO). The data are shown in Table 19.
Comparative example 4
Bisphenol fluorene polyarylether sebacamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in bisphenol fluorene polyarylether succinamide prepared in comparative example 1 with (416g, 1mol) bis (4-fluorobenzoyl) decanediamine (BFBD). The data are shown in Table 19.
Watch 19
Comparative example 5
Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene, (352g, 1mol)4,4' -diphenylmethylene bisphenol (also known as bisphenol BP, DHTPM) and 1500ml azomethyl pyrrolidone into a reaction vessel, then dehydrating at the temperature of 170 ℃ for 3h under the protection of nitrogen, and reacting at the temperature of 200 ℃ for 8h to obtain a viscous polymer solution, cooling the solution to 120 ℃, and pouring water while stirring to separate out a gray thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the purified bisphenol BP polyarylether succinamide. The data are shown in Table 20.
Comparative example 6
Bisphenol BP polyarylether adipamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in the bisphenol BP polyarylether succinamide prepared in comparative example 5 with (360g, 1mol) bis (4-fluorobenzoyl) hexanediamine (BFBH). The data are shown in Table 20.
Comparative example 7
Bisphenol BP polyarylether octanediamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in bisphenol BP polyarylether succinamide prepared in comparative example 5 with (388g, 1mol) bis (4-fluorobenzoyl) octanediamine (BFBO). The data are shown in Table 20.
Comparative example 8
Bisphenol BP polyarylether sebacamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in bisphenol BP polyarylether succinamide prepared in comparative example 5 with (416g, 1mol) bis (4-fluorobenzoyl) decanediamine (BFBD). The data are shown in Table 20.
Comparative example 9
Adding (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB), (276g, 2mol) potassium carbonate, 200ml toluene, (290g, 1mol)4,4' - (1-phenylethyl) bisphenol (also known as bisphenol AP, PEBP) and 1500ml azomethyl pyrrolidone into a reaction container, then dehydrating and reacting for 3h at the temperature of 170 ℃ under the protection of nitrogen, then reacting for 8h at the temperature of 200 ℃ to obtain a viscous polymer solution, cooling the solution to 120 ℃, pouring into water while stirring, and separating out a white thin strip-shaped polymer crude product; washing the polymer with water and ethanol, drying at 80 ℃ for 8h, crushing, washing with deionized water and ethanol respectively, and drying at 100 ℃ for l0h to obtain the purified bisphenol AP polyarylether succinamide. The data are shown in Table 21.
Comparative example 10
Bisphenol AP polyaryletheradipamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in the bisphenol AP polyaryletherbutanediamine prepared in comparative example 9 with (360g, 1mol) bis (4-fluorobenzoyl) hexanediamine (BFBH). The data are shown in Table 21.
Comparative example 11
Bisphenol AP polyaryletheroctanediamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in bisphenol AP polyaryletherbutanediamide prepared in comparative example 9 with (388g, 1mol) bis (4-fluorobenzoyl) octanediamine (BFBO). The data are shown in Table 21.
Comparative example 12
Bisphenol AP polyarylether sebacamide was prepared by replacing (332g, 1mol) bis (4-fluorobenzoyl) butanediamine (BFBB) in the bisphenol AP polyarylether succinamide prepared in comparative example 9 with (388g, 1mol) bis (4-fluorobenzoyl) decanediamine (BFBD). The data are shown in Table 21.
TABLE 21
Claims (10)
1. An intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide is characterized in that the main molecular structure general formula of the polymer is as follows:
wherein: m, n are mole percentages, m + n is 100 and m and n are not both 0;
any one of them.
2. An inherently flame retardant semi-aromatic copolymerized aryl ether amide according to claim 1, characterized in that:
when n in the formula I is 5-30 mol%, namely Ar2The mol percentage content of the aromatic polyether amide is 2.5-15 mol%, and the prepared semi-aromatic copolymerized aromatic ether amide has the characteristic viscosity number [ eta ] of]0.69-1.01dL/g, the limiting oxygen index is 30.0-45.5%, the UL-94 vertical combustion grade is V-2-V-0 grade, and the tensile strength is 68-108 MPa;
when n in the formula II is 5-30 mol%, namely R2The mol percentage content of the aromatic polyether amide is 2.5-15 mol%, and the prepared semi-aromatic copolymerized aromatic ether amide has the characteristic viscosity number [ eta ] of]0.65-0.98dL/g, limit oxygen index of 26.8-38.5%, UL-94 vertical burning grade of V-2-V-0 grade, and tensile strength of 65-105 MPa.
3. An inherently flame retardant semi-aromatic copolymerized aryl ether amide according to claim 1 or 2, characterized in that: structure Ar1From the diphenolsAny one of:
structure Ar2Any one of the diphenols from:
structure R1Any one of the following semi-aromatic difluorodiamides:
structure R2Any one from the following difluorodiamides:
4. a process for the preparation of an inherently flame retardant semi-aromatic copolyarylamide, as claimed in claim 3, wherein:
(1) when the intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide as shown in the formula one is prepared, the method comprises the following steps:
in a reaction vessel, adding the obtained Ar1Any one of diphenol DHTPM, FDP or PEBP, Ar obtained by the above2Any one of diphenol DOPO-HQ, 2DOPO-DMSi or 2DOPO-DPSi, the obtained R1Under the protection of inert gas, heating and keeping a certain temperature for reaction to obtain a solution containing the copolymer as shown in the formula I, and purifying to obtain the intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide as shown in the formula I;
(2) when the intrinsic flame-retardant semi-aromatic copolymerized aromatic ether amide as shown in the formula II is prepared, the method comprises the following steps:
in a reaction vessel, adding the obtained Ar1Any one of diphenols DHTPM, FDP or PEBP, said R2Any one of the difluorodiamide BFBPSi or BFPPO, the obtained R1Under the protection of inert gas, heating and keeping a certain temperature for reaction to obtain liquid containing the copolymer as shown in the formula II, and purifying to obtain the intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide as shown in the formula II.
5. A process for the preparation of an inherently flame retardant semi-aromatic copolyarylamide as claimed in claim 4, wherein: addition of said to obtain Ar2The molar percentage of any diphenol in the total reaction raw materials is 2.5-15 mol%, and the R is obtained by adding2The molar percentage of any one of the difluorodiamides in the total reaction raw materials is 2.5-15 mol%.
6. A process for the preparation of an inherently flame retardant semi-aromatic copolyarylamide as claimed in claim 4 or 5, wherein: the reaction conditions of the reaction are as follows: the temperature is controlled at 190 ℃ for dehydration reaction for 2-4h, and the temperature is controlled at 190 ℃ for further reaction for 6-12 h.
7. A process for the preparation of an inherently flame retardant semi-aromatic copolyarylamide, as claimed in claim 6, wherein:
the catalyst is one of sodium carbonate and potassium carbonate;
the dehydrating agent is toluene;
the inert gas is nitrogen;
the high boiling point solvent is one of N-methyl pyrrolidone and sulfolane.
8. A method as claimed in claim 4 or5 or 7, the preparation method of the intrinsic flame-retardant semi-aromatic copolymerized aryl ether amide is characterized in that: to obtain Ar2The phosphorus/silicon-containing diphenol 2DOPO-DMSi or 2DOPO-DPSi is prepared by the following steps:
dissolving 10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ) in an organic solvent in a reaction vessel, and dropwise adding a dichlorosilane solution while keeping a certain temperature; an acid-binding agent is also required to be added, and the acid-binding agent is triethylamine; after the dichlorosilane is dripped, the reaction is carried out at a certain temperature to generate reaction liquid containing the phosphorus/silicon-containing diphenol, and the phosphorus/silicon-containing diphenol is obtained after purification.
9. A process for the preparation of an inherently flame retardant semi-aromatic copolyarylamide as claimed in claim 4 or 5 or 7, wherein: said to obtain R2The silicon-containing or phosphorus-containing difluoro diamide BFBPSi or BFPPO is prepared by the following steps:
dissolving silicon-containing diamine or phosphorus-containing diamine in dichloromethane at room temperature; adding dichloromethane into a reaction container, dissolving p-fluorobenzoyl chloride into dichloromethane, and adding the prepared silicon-containing diamine or phosphorus-containing diamine solution; an acid-binding agent is also required to be added, and the acid-binding agent is triethylamine; and after the diamine solution is dripped, continuously reacting for a period of time at room temperature to generate reaction liquid containing the silicon-containing or phosphorus-containing difluorodiamide, and purifying to obtain the silicon-containing or phosphorus-containing difluorodiamide.
10. A process for the preparation of an inherently flame retardant semi-aromatic copolyarylamide in accordance with claim 8, wherein: the organic solvent is at least one of formamide, acetamide, dimethylformamide and dimethylacetamide.
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