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WO2025066980A1 - Monomère trianhydride contenant du phosphore et son procédé de préparation, et matériau polyimide, son procédé de préparation et son utilisation - Google Patents

Monomère trianhydride contenant du phosphore et son procédé de préparation, et matériau polyimide, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2025066980A1
WO2025066980A1 PCT/CN2024/119406 CN2024119406W WO2025066980A1 WO 2025066980 A1 WO2025066980 A1 WO 2025066980A1 CN 2024119406 W CN2024119406 W CN 2024119406W WO 2025066980 A1 WO2025066980 A1 WO 2025066980A1
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Prior art keywords
phosphorus
trianhydride
reaction
monomer
polyimide material
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English (en)
Chinese (zh)
Inventor
段平平
何俊鹏
邹青
练桂玫
李小波
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BYD Co Ltd
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BYD Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/08—Insulating elements, e.g. for sound insulation
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • G—PHYSICS
    • G10—MUSICAL INSTRUMENTS; ACOUSTICS
    • G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
    • G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/162—Selection of materials

Definitions

  • the present invention relates to the field of polyimide preparation, and in particular to a phosphorus-containing trianhydride monomer and a preparation method thereof, a polyimide material and a preparation method and application thereof.
  • the noise and vibration problem not only seriously affects the quietness of the car, the comfort of the passengers and the living environment of the residents along the highway, but also causes the main mechanical equipment of new energy vehicles to wear and fatigue or even fail during operation, which not only reduces the service life of the equipment but also threatens the safe operation of the car.
  • the flame retardancy of the car directly affects the driving safety. Therefore, it is necessary to improve the flame retardancy and sound absorption properties of automotive materials.
  • the CN202976826U provides a multi-layer composite sound absorbing material with flame retardant and heat insulating functions.
  • the multi-layer composite sound absorbing material is a multi-layer composite structure, including a first porous thermal insulation material layer, a hard damping sound insulation material layer and a second porous moisture-retaining material layer. It requires multiple layers or multiple materials to be composited, and the process is complicated.
  • CN103694703A discloses a polyimide foam composite material.
  • the raw materials of the polyimide foam composite material include glass microspheres and graphene sheets, and also include nano-carbon fibers.
  • a highly efficient heat-insulating and sound-absorbing lightweight material is prepared through a molding process. The disadvantage is that it cannot have both sound-absorbing and flame-retardant properties.
  • CN111087618B discloses a sound-absorbing and noise-reducing polyimide foam, which forms cavity resonance by adding hollow glass microbeads, and is combined with a subsequent material softening process and the introduction of a sound-absorbing wedge structure to improve the matching degree between the material acoustic impedance and the air acoustic impedance, thereby improving the sound-absorbing and noise-reducing performance of the polyimide.
  • this patent specifically adds a flame retardant.
  • the performance of polyimide formed by the existing technology is mainly flame retardant, and the intrinsic material performance is limited. It is difficult to achieve dual functions or multi-functions. It requires multiple layers or multiple materials to be composited, and the formula and process are complicated and the cost is high. Therefore, there is a need for a polyimide material that can simultaneously meet the requirements of flame retardant and sound absorption properties for automotive materials.
  • the purpose of the present invention is to overcome the difficulty of polyimide materials in the prior art to have both flame retardant properties and sound absorption
  • a phosphorus-containing trianhydride monomer and a preparation method thereof a polyimide material and a preparation method and application thereof are provided.
  • the phosphorus-containing trianhydride monomer has phosphorus as the main skeleton, and its structure is easy to be combined with diamine to prepare a porous polyimide material with uniform pore size distribution.
  • the present disclosure provides a phosphorus-containing trianhydride monomer in a first aspect, wherein the phosphorus-containing trianhydride monomer has a structure as shown in formula (I):
  • R2 is a residue of a substituted or unsubstituted C6 - C30 aromatic hydrocarbon which has lost two hydrogen atoms, or a residue of a substituted or unsubstituted C2 - C30 heterocyclic aromatic hydrocarbon which has lost two hydrogen atoms.
  • the second aspect of the present disclosure provides a method for preparing the aforementioned phosphorus-containing trianhydride monomer, the method comprising the following steps:
  • Grignard reagent 1 (1) in the presence of a catalyst, reacting a compound represented by the general formula Br-R 2 -OMe with magnesium powder to prepare a Grignard reagent, and then reacting the compound with phosphorus trihalide to obtain a Grignard reagent 1, wherein R 2 is a residue of a substituted or unsubstituted C 6 -C 30 aromatic hydrocarbon that has lost 2 H atoms, or a residue of a substituted or unsubstituted C 2 -C 30 heterocyclic aromatic hydrocarbon that has lost 2 H atoms;
  • the third aspect of the present disclosure provides a polyimide material, wherein the polyimide material comprises a repeating unit structure represented by formula (IV) and a connecting group R 1 between the repeating units represented by formula (IV):
  • R2 is a substituted or unsubstituted C6 - C30 aromatic hydrocarbon residue which has lost 2 Hs, or a substituted or unsubstituted C2 - C30 heterocyclic aromatic hydrocarbon residue which has lost 2 Hs, preferably a phenylene residue, a biphenyl residue which has lost 2 Hs, or a naphthalene residue which has lost 2 Hs;
  • R1 is a substituted or unsubstituted alkylene residue, a substituted or unsubstituted arylene residue, or a substituted or unsubstituted heteroarylene residue.
  • a fourth aspect of the present disclosure provides a method for preparing a polyimide material, wherein the method comprises:
  • the phosphorus-containing trianhydride monomer is the phosphorus-containing trianhydride monomer described in the first aspect.
  • a fifth aspect of the present disclosure provides a polyimide material prepared by the preparation method described in the fourth aspect.
  • a sixth aspect of the present disclosure provides an application of the polyimide material described in the third aspect or the fifth aspect in a flame retardant and sound absorbing material for automobiles.
  • the phosphorus-containing trianhydride monomer provided by the present disclosure has phosphorus as the main body and has a trianhydride structure.
  • the preparation process is simple and it is easy to prepare a foamed polyimide material with a diamine.
  • the provided phosphorus-containing trianhydride monomer is used to prepare a polyimide material, which can form an internally uniform porous structure with good mechanical properties and both flame retardant and sound absorbing properties.
  • FIG1 is a scanning electron microscope image of the porous polyimide material of Example 1;
  • FIG. 2 is a scanning electron microscope image of the porous polyimide material of Comparative Example 1.
  • the present disclosure provides a phosphorus-containing trianhydride monomer, wherein the phosphorus-containing trianhydride monomer has a structure as shown in formula (I):
  • R2 is a residue of a substituted or unsubstituted C6 - C30 aromatic hydrocarbon which has lost two hydrogen atoms, or a residue of a substituted or unsubstituted C2 - C30 heterocyclic aromatic hydrocarbon which has lost two hydrogen atoms.
  • R2 is a phenylene group, a residue of biphenyl losing two H groups, or a residue of naphthalene losing two H groups.
  • the polyimide material prepared by the phosphorus-containing trianhydride monomer having the above R2 structure has better heat resistance and flame retardancy and is more suitable for commercialization.
  • the phosphorus-containing trianhydride monomer has phosphorus as the main skeleton, and phosphorus is introduced into the anhydride monomer to obtain a novel phosphorus-containing trianhydride monomer structure, which is used to prepare polyimide materials, and helps to improve flame retardant properties while ensuring mechanical properties.
  • the phosphorus-containing trianhydride monomer is at least one of the compounds represented by the following structural formulas:
  • the second aspect of the present disclosure provides a method for preparing the aforementioned phosphorus-containing trianhydride monomer, the method comprising the following steps:
  • Grignard reagent 1 (1) in the presence of a catalyst, reacting a compound represented by the general formula Br-R 2 -OMe with magnesium powder to prepare a Grignard reagent, and then reacting the compound with phosphorus trihalide to obtain a Grignard reagent 1, wherein R 2 is a residue of a substituted or unsubstituted C 6 -C 30 aromatic hydrocarbon that has lost 2 H atoms, or a residue of a substituted or unsubstituted C 2 -C 30 heterocyclic aromatic hydrocarbon that has lost 2 H atoms;
  • the compound structure generated in each step of the preparation process of the phosphorus-containing trianhydride monomer is as follows:
  • the reaction conditions of the Grignard reaction in step (1) include: a reaction temperature of 0-120°C, preferably 0-45°C; and a reaction time of 2-24h, preferably 4-18h.
  • R2 is a phenylene group, a residue obtained by losing two H atoms of biphenyl, or a residue obtained by losing two H atoms of naphthalene.
  • the type of the catalyst is not particularly limited, and can be a conventional Grignard reagent catalyst in the art, preferably iodine and/or 1,2-dibromoethane.
  • the amount of the catalyst is not particularly limited, as long as the Grignard reagent can be prepared.
  • the product is further quenched, extracted, dried and concentrated.
  • the quenching can be performed using at least one of water, glacial acetic acid and saturated ammonium chloride solution, preferably saturated ammonium chloride solution.
  • the extraction and drying conditions are not particularly limited, and those skilled in the art can make adaptive adjustments as needed.
  • the quenched product is extracted with ethyl acetate, and the organic phase obtained by the extraction is dried and concentrated with anhydrous sodium sulfate to obtain the compound 1.
  • the molar ratio of the compound represented by the general formula Br-R 2 -OMe, magnesium powder and phosphorus trihalide is (2-4):(2-4):1, preferably (2.5-3.5):(2.5-3.5):1. Adding the reaction raw materials according to the above molar ratio for Grignard reaction can make the phosphorus trihalide react fully.
  • the compound represented by the general formula Br-R 2 -OMe is selected from at least one of 4-methoxybromobenzene, 3-methoxybromobenzene and 4-bromo-4'-methoxybiphenyl.
  • a Grignard reagent prepared by using a compound represented by the general formula Br-R 2 -OMe is subjected to a Grignard reaction with phosphorus trihalide to prepare a compound 1 with phosphorus as the main body, and subsequently a phosphorus-containing trianhydride monomer is further prepared based on compound 1, and the preparation process is simple.
  • the phosphorus trihalide is phosphorus trichloride and/or phosphorus tribromide.
  • the cyano group-containing intermediate is 4-nitrophthalonitrile.
  • the acid solution in step (2) is a mixed solution of acetic acid and hydrobromic acid, preferably a mixed solution of excess acetic acid and saturated hydrobromic acid.
  • the saturated hydrobromic acid is hydrobromic acid with a concentration of 48%.
  • the conditions of the first hydrolysis reaction include: a reaction temperature of 0-120°C, preferably 60-100°C; and a reaction time of 6-18h, preferably 8-16h.
  • step (2) further comprises extracting and separating the reaction product after the first hydrolysis reaction is cooled to room temperature.
  • the extraction is not particularly limited and may be the same as or different from the extraction described in step (1).
  • the organic phase is taken out and an alkali solution is added dropwise thereto to separate the aqueous phase.
  • the alkali solution is a strong alkali solution, preferably a sodium hydroxide solution and/or a potassium hydroxide solution.
  • the alkali solution is a 5-10 wt % sodium hydroxide solution.
  • the amount of the alkali solution is not particularly limited, as long as the aqueous phase can be separated.
  • an acid solution is added to adjust the pH of the aqueous phase solution to acidic, and the compound 2 is obtained after filtration.
  • the pH value of the aqueous phase solution after pH adjustment is less than 3, and the preferred pH value is 1-2.
  • the acid in the acid solution is a conventional acid in the art, preferably selected from at least one of hydrochloric acid, nitric acid and sulfuric acid.
  • the amount and concentration of the acid solution are not particularly limited. Those skilled in the art can make adaptive adjustments based on the pH value of the aqueous solution so that the pH value of the aqueous solution after the pH adjustment is less than 3.
  • the conditions for the heating reaction in step (3) include: a heating temperature of 80-120° C., preferably 90-110° C.; and a heating time of 2-10 h, preferably 3-8 h.
  • the molar ratio of the compound 2 to the cyano-containing intermediate in step (3) is 1:2-4, preferably 1:2-3.
  • the heating reaction of the compound 2 and the cyano-containing intermediate under the above conditions can make the heating reaction more complete.
  • step (3) further comprises a solvent, and the compound 2 and the cyano-containing intermediate are subjected to a heating reaction in the presence of a solvent.
  • the solvent is selected from at least one of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide.
  • the amount of the solvent added is not particularly limited, and those skilled in the art can make adaptive adjustments according to the conditions of the heating reaction.
  • the amount of the solvent added is such that the total molar concentration of the compound 2 and the cyano-containing intermediate in the solvent is 0.5-5 mol/L.
  • the step further includes cooling to room temperature and purifying the heating reaction product.
  • purification is performed by column chromatography.
  • the reaction conditions of the second hydrolysis in step (4) include: reaction time of 5-15h, Preferably, the time is 7-12 hours.
  • the second hydrolysis reaction is carried out at room temperature.
  • the alkaline solution in step (4) is a strong alkaline solution
  • the alkali is preferably potassium hydroxide and/or sodium hydroxide.
  • the alkaline solution is a potassium hydroxide solution with an alkali concentration of 5-10wt%.
  • the second hydrolysis product is further recrystallized.
  • the conditions for the recrystallization are not particularly limited, and glacial acetic acid is preferably used for recrystallization.
  • the conditions for the dehydration reaction in step (5) include: reaction time of 6-36 h, preferably 12-30 h; reaction temperature of 45-180° C., preferably 60-120° C.
  • the dehydration reaction is carried out in the presence of a dehydrating agent, and the dehydrating agent is a mixed solution of an acid anhydride and a corresponding acid, preferably acetic acid and acetic anhydride.
  • the dehydration reaction is carried out using the above dehydrating agent to dehydrate the carboxyl group adjacent to the terminal of the benzene ring of compound 4 to obtain a phosphorus-containing trianhydride monomer structure of formula (I).
  • step (5) further comprises recrystallizing the dehydration reaction product.
  • the conditions for the recrystallization are not particularly limited, and glacial acetic acid is preferably used for recrystallization.
  • a method for preparing a phosphorus-containing trianhydride monomer comprises the following steps:
  • Grignard reagent 1 (1) in the presence of a catalyst, reacting a compound represented by the general formula Br-R 2 -OMe with magnesium powder to prepare a Grignard reagent, and then reacting the compound with phosphorus trihalide to obtain a Grignard reagent 1, wherein R 2 is a residue of a substituted or unsubstituted C 6 -C 30 aromatic hydrocarbon that has lost 2 H atoms, or a residue of a substituted or unsubstituted C 2 -C 30 heterocyclic aromatic hydrocarbon that has lost 2 H atoms;
  • the compound represented by the general formula Br-R 2 -OMe is at least one selected from 4-methoxybromobenzene, 3-methoxybromobenzene and 4-bromo-4'-methoxybiphenyl;
  • the molar ratio of compound 2 to 4-nitrophthalonitrile in step (3) is 1:2-3.
  • the third aspect of the present disclosure provides a polyimide material, wherein the polyimide material comprises a repeating unit structure represented by formula (IV) and a connecting group R 1 between the repeating units represented by formula (IV):
  • R2 is a substituted or unsubstituted C6 - C30 aromatic hydrocarbon residue which has lost 2 Hs, or a substituted or unsubstituted C2 - C30 heterocyclic aromatic hydrocarbon residue which has lost 2 Hs, preferably a phenylene residue, a biphenyl residue which has lost 2 Hs, or a naphthalene residue which has lost 2 Hs;
  • R1 is a substituted or unsubstituted alkylene residue, a substituted or unsubstituted arylene residue, or a substituted or unsubstituted heteroarylene residue.
  • the R1 can be introduced by the added diisocyanate and/or diamine, that is, the R1 is a structural fragment other than the two isocyanate groups in the diisocyanate, or a structural fragment other than the two amine groups in the diamine.
  • the viscosity of the polyimide material is 5000-100000 mPa ⁇ s, preferably 20000-80000 mPa ⁇ s.
  • the viscosity is the viscosity of the polyimide material measured at 25° C. Measured by a rotational viscometer, which can characterize the molecular weight of the polyimide material.
  • the polyimide material further comprises an end-capping group, which can be end-capped by reacting the molecular chain end of the formed polyimide with a compound having a dicarboxylic anhydride group (phosphorus-containing trianhydride monomer of formula (I)) or an amine group (diamine).
  • a compound having a dicarboxylic anhydride group phosphorus-containing trianhydride monomer of formula (I)
  • diamine group diamine
  • dicarboxylic anhydride can be introduced for end-capping, or an excess of trianhydride monomer or diamine can be added for end-capping.
  • the polyimide material is observed under a scanning electron microscope, and it can be seen that it has a uniform porous structure, good mechanical properties, and both flame retardant properties and sound absorption properties.
  • composition and structure of the polyimide material can be determined and analyzed by infrared spectroscopy.
  • the repeating structural unit included in the polyimide material is preferably derived from a phosphorus-containing trianhydride monomer of formula (II) or (III);
  • the linking group R1 is preferably derived from diphenylmethane diisocyanate, toluene diisocyanate, 4,4'-diaminodiphenyl ether or p-phenylenediamine;
  • the end-capping group is preferably derived from a phosphorus-containing trianhydride monomer of formula (II), a phosphorus-containing trianhydride monomer of formula (III), 4,4'-diaminodiphenyl ether, or p-phenylenediamine.
  • a fourth aspect of the present disclosure provides a method for preparing a polyimide material, the method comprising:
  • the phosphorus-containing trianhydride monomer is the phosphorus-containing trianhydride monomer described in the first aspect.
  • the conditions of the polymerization reaction in step (A) include: a reaction temperature of 20-180°C, preferably 25-120°C; a reaction time of 4-24h, preferably 6-18h.
  • the aforementioned phosphorus-containing trianhydride monomer is used to carry out a polymerization reaction with diisocyanate and diamine under the above-mentioned polymerization reaction conditions to obtain a porous polyimide material with uniform pore size distribution, which has both flame retardant properties and sound absorption properties. If the polymerization reaction temperature is too high, the porous polyimide material obtained by polymerization will have uneven pores; if the polymerization reaction temperature is too low, the degree of polymerization will be low, and the mechanical properties of the product will be poor.
  • the average pore size of the polyimide material is obtained by randomly selecting 20 holes in an electron microscope image, measuring the farthest distance between the two ends of the hole, and calculating the average value.
  • the average pore size is 0.1-10 ⁇ m, preferably 0.5-5 ⁇ m.
  • the foaming condition of the polyimide material is obtained by scanning electron microscopy.
  • the phosphorus-containing trianhydride monomer reacts with diisocyanate, that is, the anhydride group reacts with the isocyanate group, and different phosphorus-containing trianhydride monomers can be connected to generate a polyimide product and carbon dioxide, and the generated carbon dioxide gas is used for foaming; the phosphorus-containing trianhydride monomer can also react with diamine, that is, the anhydride group reacts with the amino group, and the foaming amount and the pore size formed by foaming are adjusted to obtain a polyimide foam material with uniform pore size distribution. And the diamine and phosphorus-containing trianhydride monomers can also be used to form the end-capping group of the polyimide.
  • the polymerization reaction equipment of step (A) only needs to be able to carry out the polymerization reaction.
  • the polymerization reaction is carried out in a reactor.
  • the step (A) is carried out under stirring, and the stirring rate is not particularly limited, and those skilled in the art can make adaptive adjustments according to the polymerization reaction conditions.
  • the molar ratio of the phosphorus-containing trianhydride monomer, the solvent, the diisocyanate and the diamine is (0.1-0.95): (0.5-50): (0.05-0.9): 1, preferably (0.6-0.95): (3-10): (0.05-0.4): 1.
  • the phosphorus-containing trianhydride monomer, the diisocyanate, the diamine and the solvent are adjusted to a specific molar ratio for polymerization reaction, phosphorus is introduced into the polyimide material through the phosphorus-containing trianhydride monomer, and the diisocyanate is used as a foaming agent to make the pore size distribution of the polyimide material uniform.
  • the amount of the phosphorus-containing trianhydride monomer and the diamine used is excessive compared to the diisocyanate, and an end-capping group for forming the molecular chain in the polyimide is also provided.
  • the present disclosure has no particular limitation on the manner of adding the phosphorus-containing trianhydride monomer, diisocyanate and diamine, and they may be added separately or together.
  • the phosphorus-containing trianhydride monomer reacts with the diisocyanate for 0.5-2h, and then the diamine is added.
  • the polyimide material prepared by reacting in the above-mentioned addition order has good mechanical properties and can be made into a multi- The porous material is more tough.
  • the diamine can provide a residue portion other than the amino group of the diamine in the chemical composition and structure of the polyimide material, realize the connection of the phosphorus-containing trianhydride monomer, and can provide an end-capping group in the polyimide material.
  • the diamine is selected from at least one of 4,4'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 1,3-diamino-2-methylpropane, N,N-bis(4-aminophenyl)-1,4-phenylenediamine and 9,9-bis(4-aminophenyl)fluorene.
  • the diisocyanate is selected from at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
  • the diisocyanate except for the isocyanate group, the remaining residue part remains in the structure of the polyimide material to provide a connecting group for connecting the phosphorus-containing trianhydride monomer.
  • the solvent is selected from at least one of dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide.
  • the heating method of the heating in step (B) is gradient heating.
  • the gradient heating is divided into three stages, and the temperature of the latter stage is 80-120°C higher than that of the previous stage.
  • the heating temperature of the first stage is 100-200°C, preferably 130-170°C, and the heating time is 0.1-2h;
  • the heating temperature of the second stage is 200-300°C, preferably 230-270°C, and the heating time is 0.1-2h;
  • the heating temperature of the third stage is 300-400°C, preferably 330-370°C, and the heating time is 0.1-2h.
  • the carbon dioxide in the polyimide material can be slowly released to form a polyimide foam material with a uniform pore structure.
  • the types of the surfactant are well known to those skilled in the art.
  • the surfactant is selected from at least one of polyurethane rigid foam silicone oil, polyether and polysilane.
  • the amount of the surfactant is not particularly limited, and those skilled in the art can make adaptive adjustments as needed to ensure that the polyimide material is subsequently obtained.
  • the amount of the surfactant is 0.1-10wt%, preferably 1-5wt% of the polymerization product in step (A).
  • a method for preparing a polyimide material comprises:
  • the phosphorus-containing trianhydride monomer is a phosphorus-containing trianhydride monomer of formula (II) or formula (III);
  • the conditions of the polymerization reaction in step (A) include: reaction temperature of 25-120° C.; reaction time of 6-18 h;
  • the molar ratio of the phosphorus-containing trianhydride monomer, solvent, diisocyanate and diamine is (0.6-0.95): (3-10): (0.05-0.4): 1.
  • a fifth aspect of the present disclosure provides a polyimide material prepared by the preparation method described in the fourth aspect.
  • a sixth aspect of the present disclosure provides an application of the polyimide material described in the third aspect or the fifth aspect in a flame retardant and sound absorbing material for automobiles.
  • the polyimide material has both flame retardant and sound absorbing properties.
  • the impact of noise and vibration can be significantly reduced.
  • the average sound absorption coefficient can reach 0.4, the limiting oxygen index can reach 37%, and the flame retardant property is good.
  • Polyether Silok-2008N was purchased from Guangzhou Silok Company
  • Limiting oxygen index Use limiting oxygen index tester to test according to GB/T2406.2-2009;
  • Average sound absorption coefficient Use a standing wave tube to test the sound absorption coefficient of the center frequency of the six octaves of 125, 250, 500, 1000, 2000 and 4000 Hz of the test material, and take the arithmetic mean as the average sound absorption coefficient;
  • Nuclear magnetic resonance hydrogen spectrum data measured using nuclear magnetic resonance hydrogen spectrometer
  • the foaming condition was obtained by observing the polyimide material under scanning electron microscope;
  • the viscosity is the viscosity of the polyimide material measured at 25° C. It is measured by a rotational viscometer.
  • (A) phosphorus-containing trianhydride monomer 1, N,N-dimethylformamide, diphenylmethane diisocyanate, and 4,4'-diaminodiphenyl ether in a molar ratio of 0.7:10:0.3:1 are sequentially added into a reaction kettle in the order of phosphorus-containing trianhydride monomer 1, N,N-dimethylformamide, and diphenylmethane diisocyanate, and stirring is started. After reacting for 0.5 h, 4,4'-diaminodiphenyl ether is added. The reaction temperature is 25° C. and stirred for 8 hours;
  • step (B) After the reaction is completed and the temperature drops to room temperature, Silok-2008N (the amount added is 5% of the total mass of the polymerization product in step (A)) is added, and after stirring for 1 hour, the solution is poured into a mold and heated in a gradient manner at 120° C. for 1 hour, 200° C. for 2 hours, and 300° C. for 2 hours to obtain a porous polyimide material.
  • (A) phosphorus-containing trianhydride monomer 1, N,N-dimethylformamide, diphenylmethane diisocyanate, and p-phenylenediamine in a molar ratio of 0.7:10:0.3:1 are sequentially added into a reaction kettle in the order of phosphorus-containing trianhydride monomer 1, N,N-dimethylformamide, and diphenylmethane diisocyanate, and stirring is started. After reacting for 0.5 h, p-phenylenediamine is added, the reaction temperature is 45° C., and stirring is performed for 12 hours;
  • step (B) After the reaction is completed and the temperature drops to room temperature, Silok-2008N (the amount added is 5% of the total mass of the polymerization product in step (A)) is added, and after stirring for 1 hour, the solution is poured into a mold and heated in a gradient manner at 120° C. for 1 hour, 200° C. for 2 hours, and 300° C. for 2 hours to obtain a porous polyimide material.
  • (A) phosphorus-containing trianhydride monomer 1, N,N-dimethylformamide, toluene diisocyanate, and p-phenylenediamine in a molar ratio of 0.6:8:0.25:1 are sequentially added into a reaction kettle in the order of phosphorus-containing trianhydride monomer 1, N,N-dimethylformamide, and toluene diisocyanate, and stirring is started. After reacting for 0.5 h, p-phenylenediamine is added, the reaction temperature is 100° C., and stirring is performed for 24 hours;
  • step (B) After the reaction is completed and the temperature drops to room temperature, Silok-2008N (5% of the total mass of the polymerization product in step (A)) is added, and after stirring for 1 hour, the solution is poured into a mold and heated in a gradient manner of 120° C. for 1 hour, 200° C. for 2 hours, and 300° C. for 2 hours to obtain a porous polyimide material.
  • the polyimide material was prepared according to the method of Example 3, except that the phosphorus-containing trianhydride monomer 1 was replaced by an equimolar amount of the phosphorus-containing trianhydride monomer 2 to obtain a porous polyimide material.
  • the polyimide material was prepared according to the method of Example 1, except that the molar ratio of phosphorus-containing trianhydride monomer 1, toluene diisocyanate, p-phenylenediamine, and N,N-dimethylformamide in step (A) was 0.5:0.5:1:6 to obtain a porous polyimide material.
  • step (B) After cooling to room temperature, Silok-2008N (5% of the total mass of the mixed solution in step (A)) was added, and after stirring for 1 hour, the solution was poured into a mold and heated (120°C for 1 hour, 200°C for 2 hours, and 300°C for 2 hours) to obtain a porous polyimide material.
  • the polyimide material was prepared according to the method of Example 1, except that the phosphorus-containing trianhydride monomer in step (A) was replaced by an equimolar amount of (di-3,3',4,4'tetracarboxylic dianhydride benzene) phenoxyphosphine.
  • the polyimide material was prepared according to the method of Example 1, except that no diisocyanate was added in step (A).
  • Average pore size less than 3 ⁇ m is small, and greater than or equal to 3 ⁇ m is large.
  • Example 1 From the results in Table 1, it can be seen that the polyimide materials prepared in Examples 1-4 of the present disclosure have uniform internal foaming, small pore size, and significantly better flame retardancy and sound absorption properties.
  • the dianhydride used in Example 1 and Example 2 is different from the diamine, and although the main chain structure is different, the performance difference is not large, which shows that the trianhydride monomer is suitable for different polyimide structures.
  • Example 2 and Example 3 are different, but the performance is significantly better than that of the comparative example, proving that different isocyanates can also be applied to the phosphorus-containing trianhydride monomer disclosed in the present invention.
  • Example 4 changes the trianhydride monomer, and the performance difference is not much, which shows that the trianhydride monomer disclosed in the present invention has a stable effect.
  • Example 5 adjusts the molar ratio of the raw materials for preparing the polyimide material, and the limiting oxygen index is slightly lower than that of Example 1, and the foaming is poor, but the overall flame retardant and sound absorption properties are better than those of the comparative example.
  • FIG. 1 is a scanning electron microscope image of the porous polyimide material of Example 1. It can be observed in FIG. 1 that the pore size of the polyimide material of Example 1 is small and evenly distributed.
  • Comparative Example 1 The one-dimensional rigid structure in Comparative Example 1 is not conducive to foaming, the pore size is larger than that of Examples 1-4, and the sound absorption coefficient is low. Comparative Example 1 does not contain phosphorus, and the limiting oxygen index is low.
  • FIG2 is a scanning electron microscope image of the porous polyimide material of Comparative Example 1. FIG2 shows that the pore size of the polyimide material of Comparative Example 1 is large, and the internal pore size distribution is uneven.
  • Comparative Example 2 does not use the phosphorus-containing trianhydride monomer disclosed in the present invention, and the prepared polyimide material has a larger pore size and non-uniform foaming.
  • the limiting oxygen index and the average sound absorption coefficient are both low, and the flame retardancy and sound absorption performance are poor.
  • no diisocyanate is added during the preparation of the polyimide, no bubbles are generated, and the sound absorption performance is not good.

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Abstract

L'invention concerne un monomère de trianhydride contenant du phosphore et son procédé de préparation, et un matériau polyimide, son procédé de préparation et son utilisation. Le monomère de trianhydride contenant du phosphore a une structure telle que représentée dans la formule (I) : Formule (I), dans laquelle R2 est un résidu d'un hydrocarbure aromatique C6-C30 substitué ou non substitué qui a perdu deux atomes H, ou un résidu d'un hydrocarbure aromatique C2-C30 hétérocyclique substitué ou non substitué qui a perdu deux atomes H. En utilisant le monomère trianhydride contenant du phosphore fourni pour préparer un matériau polyimide, une structure poreuse intérieurement uniforme peut être formée, et le matériau polyimide présente de bonnes propriétés mécaniques et permet à la fois la propriété ignifuge et la propriété d'absorption acoustique.
PCT/CN2024/119406 2023-09-27 2024-09-18 Monomère trianhydride contenant du phosphore et son procédé de préparation, et matériau polyimide, son procédé de préparation et son utilisation Pending WO2025066980A1 (fr)

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CN118221734A (zh) * 2023-09-27 2024-06-21 比亚迪股份有限公司 含磷三酐单体及其制备方法、聚酰亚胺材料及其制备方法与应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5066760A (en) * 1989-07-13 1991-11-19 Lenzing Aktiengesellschaft Mixed polyimides and process for preparing them
JP2011173806A (ja) * 2010-02-23 2011-09-08 Manac Inc リン含有ジアミン化合物および難燃性ポリイミド
US10294255B1 (en) * 2015-08-07 2019-05-21 The United States Of America As Represented By The Secretary Of The Air Force Multifunctional crosslinking agent, crosslinked polymer, and method of making same
US11504899B1 (en) * 2019-09-30 2022-11-22 United States Of America As Represented By The Secretary Of The Air Force Method for fabricating lightly crosslinked polyimides with phenylethynyl pendants for shape-memory effect and programmed enhancement in Tg and modulus
US20220388222A1 (en) * 2019-09-30 2022-12-08 Government Of The United States, As Represented By The Secretary Of The Air Force Multiphenylethynyl-Containing and Lightly Crosslinked Polyimides Capable of Memorizing Shapes and Augmenting Thermomechanical Stability
US11613051B1 (en) * 2019-09-30 2023-03-28 United States Of America As Represented By The Secretary Of The Air Force Shape-memory polyimide nanocomposites and fabrication of same
CN118221734A (zh) * 2023-09-27 2024-06-21 比亚迪股份有限公司 含磷三酐单体及其制备方法、聚酰亚胺材料及其制备方法与应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5066760A (en) * 1989-07-13 1991-11-19 Lenzing Aktiengesellschaft Mixed polyimides and process for preparing them
JP2011173806A (ja) * 2010-02-23 2011-09-08 Manac Inc リン含有ジアミン化合物および難燃性ポリイミド
US10294255B1 (en) * 2015-08-07 2019-05-21 The United States Of America As Represented By The Secretary Of The Air Force Multifunctional crosslinking agent, crosslinked polymer, and method of making same
US11504899B1 (en) * 2019-09-30 2022-11-22 United States Of America As Represented By The Secretary Of The Air Force Method for fabricating lightly crosslinked polyimides with phenylethynyl pendants for shape-memory effect and programmed enhancement in Tg and modulus
US20220388222A1 (en) * 2019-09-30 2022-12-08 Government Of The United States, As Represented By The Secretary Of The Air Force Multiphenylethynyl-Containing and Lightly Crosslinked Polyimides Capable of Memorizing Shapes and Augmenting Thermomechanical Stability
US11613051B1 (en) * 2019-09-30 2023-03-28 United States Of America As Represented By The Secretary Of The Air Force Shape-memory polyimide nanocomposites and fabrication of same
CN118221734A (zh) * 2023-09-27 2024-06-21 比亚迪股份有限公司 含磷三酐单体及其制备方法、聚酰亚胺材料及其制备方法与应用

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