WO2022267730A1 - Procédé de synthèse de verre moléculaire et utilisation de celui-ci en tant que matériau à faible constante diélectrique et haute fréquence - Google Patents

Procédé de synthèse de verre moléculaire et utilisation de celui-ci en tant que matériau à faible constante diélectrique et haute fréquence Download PDF

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WO2022267730A1
WO2022267730A1 PCT/CN2022/092261 CN2022092261W WO2022267730A1 WO 2022267730 A1 WO2022267730 A1 WO 2022267730A1 CN 2022092261 W CN2022092261 W CN 2022092261W WO 2022267730 A1 WO2022267730 A1 WO 2022267730A1
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group
substituted
unsubstituted
alkyl
halogen
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PCT/CN2022/092261
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Chinese (zh)
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房强
黄港
孙晶
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中国科学院上海有机化学研究所
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/34—Monomers containing two or more unsaturated aliphatic radicals

Definitions

  • the invention relates to the field of high-performance low-permittivity thermosetting resin materials, in particular to a directly thermally curable "molecular glass” monomer, its preparation method and its application as a high-frequency low-permittivity material.
  • 5G communication technology will rely more on new materials than any previous generation, mainly because of the high signal transmission speed (about 10Gbps) and low signal delay ( ⁇ 1ms) of 5G communication. And features such as multi-user access.
  • sub-6GHz and millimeter waves will be used for signal transmission.
  • millimeter wave frequency when the electric field passes through the medium, the heat loss due to the alternating polarization of the medium molecules and the back and forth collision of the lattice will be intensified.
  • the signal transmission loss in communication technology mainly includes conductor loss (T LC ) and dielectric loss (T LD ), and the dielectric loss T LD is related to the dielectric constant (D k ) and dielectric loss (D f ) of the dielectric material.
  • D k dielectric constant
  • D f dielectric loss
  • K represents the coefficient
  • f represents the frequency
  • c represents the speed of light. Therefore, in high-frequency communication, in order to reduce signal transmission loss, the Dk and Df values of dielectric materials must be reduced as much as possible.
  • these dielectric materials are also required to have high mechanical strength, high Young's modulus, high breakdown voltage, low leakage, high thermal stability, good bond strength with conductors, low water absorption and good Processing performance.
  • materials widely used in 5G communication technology include polytetrafluoroethylene (PTFE), modified polyphenylene ether (MPPE), modified polyimide (MPI), LCP, etc. Due to the low elastic modulus, poor conductor adhesion and high linear thermal expansion coefficient of PTFE, its application in ultra-thin circuit boards is limited. MPPE substrate has excellent dielectric properties, but its thermal stability and dimensional stability are poor, making it difficult to meet high material processing requirements. Therefore, there is an urgent need to develop new high-frequency low-dielectric constant materials to meet the application requirements of 5G communications.
  • film-forming property is a key performance parameter.
  • polymer materials with an amorphous state are generally used, and uniform and dense thin films can be formed by solution processing methods, but polymers have The disadvantages of uncontrollable synthesis and difficult purification.
  • Small molecular compounds can well solve the problems of uncontrollable synthesis and difficult purification, but because the molecular weight of general small molecular compounds is not large enough, the formed thin film is thermally unstable and prone to aggregation and crystallization. Therefore, preparing a compound that is easy to purify and can form an amorphous film can effectively solve this problem.
  • Molecular glass is a class of small molecular compounds with relatively large molecular weight and amorphous characteristics like polymers at room temperature. It has the characteristics of controllable small molecule synthesis, easy purification and amorphous polymer. When it is solidified at high temperature, it will not melt and flow like ordinary small molecule monomers, which will affect the performance of the film, and has excellent processing advantages. Therefore, the development of molecular glasses that can be used as low dielectric constant materials has important application value.
  • the object of the present invention is to provide a "molecular glass" monomer with excellent processability and its preparation method, and a resin with excellent high frequency and low dielectric properties prepared from the monomer and its application.
  • Each R is independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1 -C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C1-C15 alkylsilyl, wherein the substitution means that one or more hydrogen atoms on the group are replaced by substituents selected from the following groups: halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, unsubstituted or 1-3 hydrogen atoms on the benzene ring are substituted by a substituent selected from the following group: halogen, C1-C4 alkyl;
  • Each R is independently selected from the group consisting of C3 - C8 benzocycloalkenyl, C2-C6 alkenylphenyl;
  • R 3 and R 4 are each independently selected from the following group: hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl, wherein the substitution refers to one or more Each hydrogen atom is replaced by a substituent selected from the group consisting of halogen, C1-C4 alkyl.
  • the halogen is fluorine
  • each R 1 is the same or different, preferably the same.
  • each R 1 is independently located at the meta or para position of the carbon atom on the benzene ring connected to the triazine, preferably the para position.
  • each R 2 is the same or different, preferably the same.
  • R 3 and R 4 are the same or different, preferably the same.
  • each R1 is independently selected from the following group: hydrogen, halogen, C1 -C6 alkyl, C1-C6 haloalkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C1 -C15 alkylsilyl;
  • Each R is independently selected from the group consisting of: C3 - C6 benzocycloalkenyl, C2-C4 alkenylphenyl;
  • R 3 and R 4 are the same or different. When they are the same, they are selected from the following groups: hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, substituted or unsubstituted C6-C10 aryl; when they are different, R 3 and One of R 4 is C1-C6 alkyl and C1-C6 haloalkyl, and the other of R 3 and R 4 is substituted or unsubstituted C6-C10 aryl, wherein the substitution refers to one or Multiple hydrogen atoms are substituted by substituents selected from the group consisting of halogen, C1-C4 alkyl.
  • each R1 is independently selected from the following group: hydrogen, fluorine, C1 -C4 alkyl, C1-C4 fluoroalkyl, C1-C12 alkylsilyl;
  • Each R 2 is independently selected from the group consisting of benzocyclobutenyl, styryl;
  • R 3 and R 4 are the same or different. When they are the same, they are selected from the following groups: hydrogen, C1-C4 alkyl, C1-C4 fluoroalkyl, and substituted phenyl; when they are different, one of R 3 and R 4 C1-C4 alkyl and C1- C4 fluoroalkyl, the other of R3 and R4 is a substituted phenyl group, wherein the substitution means that one or more hydrogen atoms on the group are selected from the following group Substituent substitution: fluorine, C1-C4 alkyl.
  • each R1 is independently selected from the following group: hydrogen, fluorine, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, triethylsilyl, triiso Propylsilyl, Tributylsilyl, Trifluoromethyl.
  • benzocyclobutenyl is N-(2-aminoethyl)-2-aminoethyl
  • the styryl is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • R 3 and R 4 are the same or different, and when they are the same, they are selected from the following groups: hydrogen, trifluoromethyl, methyl, and substituted phenyl; when they are different, they are methyl and substituted phenyl , trifluoromethyl and substituted phenyl groups.
  • the substitution means that the group is substituted by one or more substituents selected from the following substituents: C1-C4 alkyl and fluorine atoms.
  • each group is a specific group described in each compound of the embodiment.
  • the monomer is selected from the following group:
  • the glass transition temperature of the monomer is 50-100°C, preferably 70-90°C.
  • R is selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1 -C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C1-C15 alkylsilyl, wherein said Substitution means that one or more hydrogen atoms on the group are replaced by substituents selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, unsubstituted or benzene ring 1-3 hydrogen atoms are substituted by substituents selected from the following phenyl group: halogen, C1-C4 alkyl;
  • R is selected from the group consisting of: C3 - C8 benzocycloalkenyl, C2-C6 alkenylphenyl;
  • R 3 and R 4 are each independently selected from the following group: hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl, wherein the substitution refers to one or more Each hydrogen atom is replaced by a substituent selected from the group consisting of halogen, C1-C4 alkyl.
  • R 1 , R 2 , R 3 , and R 4 are as defined in the first aspect of the present invention.
  • R is selected from the following group: C1 -C4 alkyl, C2-C4 alkenyl, C1-C12 alkylsilyl;
  • R 2 is selected from the group consisting of benzocyclobutenyl, styryl;
  • R 3 and R 4 are the same or different. When they are the same, they are selected from the following groups: hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, substituted phenyl; when they are different, one of R 3 and R 4 is C1 -C4 alkyl and C1- C4 haloalkyl, the other of R3 and R4 is a substituted phenyl group, wherein the substitution means that one or more hydrogen atoms on the group are replaced by a substituent selected from the following group: Fluorine, C1-C4 alkyl.
  • the molar ratio of the compound of formula II to the compound of formula III is 1:0.2-2, preferably 1:0.4-0.1, more preferably 1:0.5-0.6.
  • the first inert solvent is a mixed solvent of an organic solvent and water, wherein the organic solvent is selected from the group consisting of dichloromethane, chloroform, dichloroethane, toluene, xylene, or a combination thereof.
  • the volume ratio of the organic solvent to water in the first inert solvent is 1:1.0-10.0, preferably 1:1.0-2.0, for example 1:1.5.
  • the molar volume ratio of the compound of formula II to the first inert solvent is 0.05-0.3mol/L, preferably 0.06-0.2mol/L, such as 0.1mol/L, 0.12mol/L, 0.15mol /L, 0.2mol/L.
  • the method is carried out in a water-oil two-phase system.
  • the method is carried out in the presence of a phase transfer catalyst.
  • the phase transfer catalyst is selected from the group consisting of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctyl Methylammonium chloride, dodecyltrimethylammonium chloride, cetyltrimethylammonium bromide, or combinations thereof.
  • the molar ratio of the phase transfer catalyst to the compound of formula III is 0.001 to 0.1, such as 0.005, 0.01, 0.05, 0.08.
  • the base is an inorganic base selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, cesium carbonate, or a combination thereof.
  • the molar ratio of the inorganic base to the compound of formula II is 1.0-5.0:1, such as 2:1, 3:1, 4:1.
  • step (a) includes:
  • the aqueous phase includes a compound of formula III, an alkali and water;
  • the oil phase includes a compound of formula II, an organic solvent and a phase transfer catalyst
  • the step (a) includes: first adding the compound of formula III, alkali and water; then adding the compound of formula II, an organic solvent and a phase transfer catalyst, heating and stirring for reaction to obtain the compound of formula I.
  • step (a) is carried out at 0-100°C, preferably at 20-80°C, more preferably at 30-60°C.
  • reaction time of step (a) is 2-24h, preferably 4-16h, more preferably 6-16h.
  • the compound of formula I is obtained by extraction, drying, desolventization under reduced pressure, and column chromatography.
  • R is selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1 -C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C1-C15 alkylsilyl, wherein said Substitution means that one or more hydrogen atoms on the group are replaced by substituents selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, unsubstituted or benzene ring 1-3 hydrogen atoms are substituted by substituents selected from the following phenyl group: halogen, C1-C4 alkyl;
  • R 2 is selected from the group consisting of C3-C8 benzocycloalkenyl, C2-C6 alkenylphenyl.
  • R 1 and R 2 are as defined in the first aspect of the present invention.
  • R 1 is located at the meta or para position of the carbon atom on the benzene ring connected to the triazine, preferably the para position.
  • R is selected from the following group: C1 -C4 alkyl, C2-C4 alkenyl, C1-C12 alkylsilyl;
  • R 2 is selected from the group consisting of benzocyclobutenyl, styryl.
  • the compound is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • a method for preparing a triazine compound as described in the third aspect of the present invention comprising the following steps:
  • the compound of formula A is used to perform a substitution reaction with a compound of formula B, and then with a compound of formula C to obtain a compound of formula II; or
  • R is selected from the group consisting of hydrogen, halogen, substituted or unsubstituted C1 -C6 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C1-C15 alkylsilyl, wherein said Substitution means that one or more hydrogen atoms on the group are replaced by substituents selected from the group consisting of halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, unsubstituted or benzene ring 1-3 hydrogen atoms are substituted by substituents selected from the following phenyl group: halogen, C1-C4 alkyl;
  • R is selected from the group consisting of: C3 - C8 benzocycloalkenyl, C2-C6 alkenylphenyl;
  • X 1 and X 2 are each independently halogen, preferably Cl or Br.
  • said step (1) includes the following steps:
  • the intermediate 1 is obtained by performing a substitution reaction with a compound of formula A and a compound of formula B;
  • R 1 and R 2 are as defined in the first aspect of the present invention.
  • the inert gas is selected from the group consisting of nitrogen and argon.
  • the compound of formula B is selected from the group consisting of 4-methylphenylmagnesium bromide, 4-methylphenylmagnesium chloride, 3-methylphenylmagnesium bromide, 4-isopropyl Phenylmagnesium bromide, 4-tert-butylphenylmagnesium bromide, 4-trimethylsilylphenylmagnesium bromide, or combinations thereof.
  • the molar ratio of the compound of formula A to the compound of formula B is 1:1-5, such as 1:1, 1:1.5, 1:2.
  • step (a1) is carried out at -20-10°C, preferably -10-5°C, more preferably -5-0°C.
  • reaction time of step (a1) is 10-30h, preferably 15-25h.
  • the step (a1) includes: adding the compound of formula B to the compound of formula A dropwise under the protection of an inert gas to react to obtain intermediate 1.
  • step (a1) after the quenching of the reaction in step (a1), extraction is performed, the solvent is removed by concentration, and intermediate 1 is obtained by column chromatography.
  • the compound of formula C is selected from the group consisting of 4-benzocyclobutenylmagnesium bromide, 4-styrylmagnesium bromide, or combinations thereof.
  • the molar ratio of the intermediate 1 to the compound of formula C is 1:0.5-3, such as 1:1, 1:1.5, 1:2, 1:3.
  • the second inert solvent is selected from the group consisting of chloroform, toluene, acetone, tetrahydrofuran, dioxane, or combinations thereof, preferably tetrahydrofuran.
  • step (b1) is carried out at 5-60°C, preferably 10-50°C, more preferably 10-45°C.
  • reaction time of step (b1) is 2-15h, preferably 5-10h, more preferably 6-8h.
  • step (b1) includes: adding dropwise a solution of the compound of formula C in the second inert solvent to the solution of intermediate 1 in the second inert solvent to obtain the compound of formula II.
  • the concentration of the intermediate in the solution of the intermediate 1 in the second inert solvent is 0.1-0.8mol/L, preferably 0.2-0.6mol/L, such as 0.3mol/L, 0.35mol/L L, 0.4mol/L, 0.5mol/L.
  • the concentration of the compound of formula C in the solution of the compound of formula C in the second inert solvent is 0.3-1.2mol/L, preferably 0.5-1mol/L, such as 0.6mol/L, 0.7mol/L L, 0.8mol/L, 0.9mol/L.
  • step (b1) after the reaction in step (b1), the solvent is removed under reduced pressure, and the compound of formula II is obtained by column chromatography.
  • said step (2) includes the following steps:
  • R 1 and R 2 are as defined in the first aspect of the present invention.
  • reaction conditions of step (b1) are the same as those of step (a2); the reaction conditions of step (b2) are the same as those of step (a1).
  • the preparation method of the compound of formula III comprises the following steps:
  • R 3 and R 4 are each independently selected from the following group: hydrogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C6-C10 aryl, wherein the substitution refers to one of the or multiple hydrogen atoms are substituted by substituents selected from the following group: halogen, C1-C4 alkyl;
  • Y is halogen, preferably Cl, Br.
  • R 3 and R 4 are the same or different, and when they are the same, they are selected from the following groups: hydrogen, trifluoromethyl, methyl, and substituted phenyl; when they are different, they are methyl and substituted phenyl , trifluoromethyl and substituted phenyl groups.
  • the substitution means that the group is substituted by one or more substituents selected from the following substituents: C1-C4 alkyl and fluorine atoms.
  • R 3 and R 4 are as defined in the first aspect of the present invention.
  • the compound of formula D is a bisphenol compound substituted by R 3 and R 4 , preferably bisphenol A or bisphenol AF.
  • the molar ratio of the compound of formula D to the compound of formula E is 3-5:1.
  • the third inert solvent is selected from the group consisting of chloroform, toluene, acetone, tetrahydrofuran, dioxane, or combinations thereof, preferably acetone.
  • the molar volume ratio of the compound of formula D to the third inert solvent is 0.1-1 mol/L, such as 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L.
  • the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, or combinations thereof, preferably potassium carbonate.
  • the molar ratio of the compound of formula D to the base is 0.1-1, preferably 0.2-0.5, such as 0.2, 0.3, 0.4, 0.5.
  • step (1) is carried out at 40-100°C, preferably at 50-80°C, more preferably at 60-70°C.
  • reaction time of step (1) is 6-48h, preferably 12-24h.
  • the heating temperature in step (2) is 160-250°C.
  • reaction time of the reaction is 6-48h, preferably 9-24h.
  • the compound of formula III is obtained by rectifying under reduced pressure and separated by column chromatography.
  • a cured product is provided, the cured product is formed by cross-linking reaction of cured raw materials;
  • the curing raw material includes the "molecular glass” monomer described in the first aspect of the present invention.
  • the cured product is formed by cross-linking the cured raw material through a D-A reaction between double bonds and cycloolefins.
  • the curing raw material includes the "molecular glass” monomer described in the first aspect of the present invention and other thermally curable monomers or polymers.
  • the curing raw material is the "molecular glass” monomer described in the first aspect of the present invention, or a blend of the "molecular glass” monomer and other thermally curable monomers or polymers .
  • the curing raw material also includes a thermally curable monomer comprising an R2 group in the structure ;
  • R 2 is selected from the group consisting of C3-C8 benzocycloalkenyl, C2-C6 alkenylphenyl, preferably benzocyclobutenyl, styryl.
  • the thermally curable monomer containing the R2 group in the structure is selected from the group consisting of benzocycloalkenes, alkenylbenzenes, acrylates, or combinations thereof, preferably benzocycloalkenes Butylene, Styrene, Allylbenzene, Methyl Acrylate, Ethyl Acrylate.
  • the curing raw material further includes thermally curable low-dielectric polymers, such as low-dielectric polyimide, polyphenylene ether, polytetrafluoroethylene, and the like.
  • thermally curable low-dielectric polymers such as low-dielectric polyimide, polyphenylene ether, polytetrafluoroethylene, and the like.
  • the mole fraction of "molecular glass" monomer in the curing raw material is 10%-100%, preferably 30%-100%, more preferably 50%-100%.
  • the curing raw material is the "molecular glass" monomer described in the first aspect of the present invention.
  • the cured product is obtained by cross-linking the "molecular glass" monomer described in the first aspect of the present invention.
  • the cured product is a three-dimensional structure obtained by a cross-linking reaction, which is a polymer.
  • the cured product is a resin.
  • the degree of crosslinking of the cured product is 50%-100%, preferably 70%-100%.
  • the cured product is insoluble and infusible, has excellent low dielectric properties, excellent thermomechanical properties, low water absorption and excellent surface smoothness, especially high frequency and low dielectric properties.
  • the cured product has one or more of the following characteristics:
  • glass transition temperature is 250 ⁇ 500 °C, preferably 300 ⁇ 400 °C, more preferably 330 ⁇ 250 °C;
  • the dielectric loss is 0.5 to 3 ⁇ 10 -3 (in the range of 5-10GHz), preferably 1 to 2.5 ⁇ 10 -3 , more preferably 1.0 to 2.3 ⁇ 10 -3 ;
  • the coefficient of thermal expansion is 40-80ppm/°C (in the range of room temperature to 300°C), preferably 60-70ppm/°C;
  • a method for preparing a cured product according to the fifth aspect of the present invention comprising the steps of: heating and curing the curing raw material to obtain a cured product;
  • the curing raw material includes the "molecular glass” monomer described in the first aspect of the present invention.
  • the curing raw material is as described in the fifth aspect of the present invention.
  • the curing raw material is cured directly or in the form of a solution dissolved in a fourth inert solvent, so as to obtain a cured product.
  • the fourth inert solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N -Dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or combinations thereof .
  • the method for preparing the cured product is a method for curing raw materials.
  • the curing is cross-linking and curing by heating (ie heat curing).
  • the curing is performed under the protection of an inert gas, wherein the inert gas is selected from the group consisting of nitrogen and argon.
  • the heat curing is carried out at 100-350°C, preferably 150-300°C.
  • the heat curing is temperature programmed curing.
  • the heat curing includes: curing at 170-190°C for 1-6 hours, then curing at 210-240°C for 3-8 hours, and then curing at 250-300°C for 0.25-2 hours.
  • the heat curing includes: curing at 170-190° C. for 1-3 hours, then curing at 210-240° C. for 3-6 hours, and then curing at 250-300° C. for 0.25-1 hour.
  • the heating and curing temperature is determined by the DSC curve of the curing raw material.
  • the heating and curing time is determined by the structure, quality and shape of the curing raw material.
  • the heating and curing further includes: before the heating and curing, slowly heating and/or mechanically vibrating the curing raw material, so as to remove air bubbles and form a dense liquid; preferably, the The temperature rise is from room temperature to 170-190°C.
  • a product which contains the cured product as described in the fifth aspect of the present invention, the "molecular glass” monomer as described in the first aspect of the present invention;
  • the article is prepared by using the cured product as described in the fifth aspect of the present invention, the "molecular glass” monomer as described in the first aspect of the present invention.
  • the product is a high-frequency low-dielectric constant material, preferably a low-dielectric film substrate material, a low-dielectric film, a low-dielectric matrix resin, and a low-dielectric packaging material.
  • the product includes: a substrate, and a film containing the cured product according to the fifth aspect of the present invention coated on the substrate.
  • the product is prepared by the following method: molding with the curing raw material as described in the fifth aspect of the present invention to obtain a preform, and then heating and curing the preform, The product described is obtained.
  • the forming is carried out by a forming process selected from the following group: pouring, solution spin coating, or solution drop coating.
  • the solution spin coating or solution drop coating includes the step of: dissolving the curing raw material or the prepolymer of the curing raw material as described in the fifth aspect of the present invention in a fourth inert solvent to form a solution , followed by spin coating or drop coating;
  • the prepolymer is an oligomer obtained by dissolving curing raw materials in a fourth inert solvent and heating and crosslinking.
  • the prepolymer still maintains good solubility in the solution and has good processability.
  • the degree of crosslinking of the prepolymer is 0.1%-50%, preferably 5%-30%.
  • the fourth inert solvent is selected from the group consisting of toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N -Dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or combinations thereof .
  • the product is selected from the group consisting of low dielectric film substrate material, low dielectric film, low dielectric constant matrix resin, Low dielectric packaging materials, high frequency low dielectric constant materials.
  • Figure 1 shows the DSC curves of molecular glass monomers M1 and M2 (heating rate 10°C/min).
  • Figure 2 shows the DMA curves of the resin sample strips cured by the molecular glass monomers M1 and M2 (heating rate 5°C/min).
  • Figure 3 shows the CTE curves of the resin sample strips cured by the molecular glass monomers M1 and M2 (heating rate 5°C/min).
  • the inventor unexpectedly developed a "molecular glass” monomer and the resin obtained after curing for the first time.
  • the "molecular glass” monomer has a rigid aryl group, a heat-curable group and a flexible allyl group.
  • the structural characteristics of "rigid and flexible” make it have excellent processing performance and maintain an amorphous state at room temperature.
  • the synthesis method of this monomer is simple, the conditions are mild, and the yield is high.
  • the resin obtained by curing the "molecular glass” monomer exhibits excellent high-frequency dielectric properties (the dielectric constant is 2.53 at 10 GHz, and the dielectric loss is 1.93 ⁇ 10 -3 ), and the glass transition temperature is high (T g >339°C), low thermal expansion coefficient (25-300°C, CTE as low as 63.0ppm/°C), low water absorption (as low as 0.19%), can be used as high-performance matrix resin or packaging material for high-frequency communication, large Scale integrated circuits, microelectronics industry and aerospace and other fields.
  • 'molecular glass' monomer and “molecular glass” are used interchangeably, and refer to the reaction of disubstituted 1,3,5-triazine and bisphenol as shown in formula (I). molecular compound.
  • C3-C8 benzocycloalkenyl refers to a group formed by a polycyclic benzocycloalkane composed of a benzene ring and a cycloalkane with 3-8 carbon atoms when a hydrogen atom is lost on the benzene ring, For example, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl and the like.
  • benzocyclobutenyl refers to a group formed by losing a hydrogen atom on the benzene ring of benzocyclobutene, for example or similar groups.
  • C2-C6 alkenylphenyl refers to a group formed by the loss of a hydrogen atom on the benzene ring, such as styryl, 1- propenylphenyl, 1-butenylphenyl, etc.
  • C1-C15 alkylsilyl means Wherein R 1 , R 2 , and R 3 are each independently the following C1-C6 alkyl groups, such as trimethylsilyl, triethylsilyl, triisopropylsilyl, tributylsilyl, etc.
  • halogen refers to F, Cl, Br or I.
  • C1-C6 alkyl refers to a linear or branched alkyl group comprising 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, iso Butyl, tert-butyl, neopentyl, tertyl, or similar groups.
  • C1-C4 alkyl has a similar meaning.
  • C2-C6 alkenyl refers to a straight-chain or branched alkenyl group with 2-6 carbon atoms containing a double bond, including non-limiting ethenyl, propenyl, butenyl , Isobutenyl, Pentenyl and Hexenyl etc.
  • C2-C4 alkenyl has a similar meaning.
  • C2-C4 alkynyl refers to a straight-chain or branched-chain alkynyl group with 2-4 carbon atoms containing a triple bond, including without limitation ethynyl, propynyl, butynyl base, isobutynyl, etc.
  • aromatic ring or “aryl” has the same meaning, preferably “C6-C10 aryl”.
  • C6-C10 aryl refers to an aromatic ring group having 6-10 carbon atoms without heteroatoms in the ring, such as phenyl, naphthyl and the like.
  • substituted means that one or more hydrogen atoms on a specific group are replaced by a specific substituent.
  • the specific substituents are the corresponding substituents described above, or the substituents appearing in each embodiment.
  • a substituted group may have a substituent selected from a specific group at any substitutable position of the group, and the substituents may be the same or different at each position.
  • substituents contemplated by this invention are those that are stable or chemically feasible.
  • the substituents are for example (but not limited to): halogen, hydroxyl, carboxyl (-COOH), C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C8 cycloalkyl, 3- to 12-membered heterocyclic group, aryl group, heteroaryl group, C1-C8 aldehyde group, C2-C10 acyl group, C2-C10 ester group, amino group, C1-C6 alkoxy group, C1-C10 sulfonyl group, etc.
  • the term 1-6 refers to 1, 2, 3, 4, 5 or 6. Other similar terms have similar meanings.
  • Molecular glass is a small molecular compound with relatively large molecular weight. It exhibits the same amorphous characteristics as polymers at room temperature. It has the characteristics of controllable synthesis of small molecules, easy purification and amorphous polymers. It is soluble in solvents It has good film-forming properties and can be directly coated on a glass plate to form a thin film. It will not melt and flow like ordinary small molecule monomers when it is cured at high temperature, and has excellent processing performance.
  • the present invention utilizes the characteristics of strong modifiability, good thermal stability and excellent dielectric properties of triazine ring, and introduces aryl group and curable group through Grignard reaction to form a rigid glass.
  • the three-dimensional structure has a large free volume, which can effectively reduce the dielectric constant and prevent the dense packing between molecules to form crystals.
  • diallyl bisphenol compound is used as a linker to connect two molecules of disubstituted triazine monomers to increase the molecular weight.
  • the introduction of flexible allyl groups can reduce the crystallinity of molecules and increase the crosslinking density.
  • the bisphenol structure is linked by the sp carbon, and the chemical bond distribution of the tetrahedron can further increase the disorder of the molecule.
  • the structure design of molecular glass monomer is ingenious, the synthesis steps are simple, and the raw materials are easy to obtain, so it has a good application prospect.
  • the resin formed by the molecular glass of the present invention is infusible and insoluble after solidification, has excellent heat resistance and low water absorption, and especially exhibits very low dielectric constant and dielectric loss at high frequencies. It exhibits low dielectric constant and dielectric loss at 10GHz, and has high modulus, low thermal expansion coefficient, low water absorption and good heat resistance. It can be used as a low dielectric constant matrix resin or packaging material for high In the fields of frequency communication, microelectronics industry and aerospace.
  • the "molecular glass” monomer of the present invention contains rigid aryl groups and thermosetting groups, as well as flexible acrylic groups, which will not crystallize like small molecules while reducing dielectric loss;
  • the "molecular glass" monomer of the present invention has excellent processing properties. After being dissolved in a solution, it can be directly spin-coated or drip-coated, and then thermally cured to obtain a resin. The processing technology is extremely advantageous.
  • the "molecular glass" monomer of the present invention can be used as an excellent high-frequency dielectric material after curing, showing high heat resistance, low water absorption (as low as 0.19%), and a high glass transition temperature (T g >339°C), low thermal expansion coefficient (25-300°C, CTE as low as 63.0ppm/°C) and exhibits excellent dielectric properties at 10GHz high frequency (dielectric constant as low as 2.53, dielectric loss as low as 1.93 ⁇ 10 -3 ).
  • a new type of high-temperature curing resin can be obtained after curing the "molecular glass" monomer of the present invention, which can be used as a high-performance matrix resin or packaging material for high-frequency communication, large-scale integrated circuits, microelectronics industry, aerospace, etc. in the field.
  • DMA Dynamic thermomechanical analysis
  • the dielectric constant and dielectric loss were measured by a separate dielectric resonator (QWED) at room temperature at a frequency of 5/10 GHz.
  • the cured resin sheet was dried under vacuum at 100°C to a constant weight, and then soaked in boiling water for several days. Calculate the water absorption rate according to the weight increase of the cured resin sheet after soaking.
  • Embodiment 1 Synthesis of double substituted 1,3,5-triazine S1
  • Embodiment 2 Synthesis of Molecular Glass Monomer M1
  • the tube furnace is a semi-closed system filled with high-purity nitrogen gas with a constant flow rate of 0.3L/min.
  • the temperature is raised to 190°C for 2 hours, and then solidified at 240°C. Cured for 4 hours, and cured for 0.5 hours at 260°C to obtain cured resin P1.
  • the glass transition temperature of the monomer M1 measured by DSC is 69° C., and the results are shown in FIG. 1 . Grind the cured sample into a uniform disc, and test its dielectric properties.
  • Example 6 The curing of "molecular glass” monomer M2 and the performance research of its corresponding resin
  • the target monomer M2 prepared in Example 4 was put into a tube furnace, and the temperature was raised to 190° C. for 2 hours, 240° C. for 4 hours, and 260° C. for 0.5 hours to obtain cured resin P2.
  • the glass transition temperature of the monomer M2 measured by DSC is 84° C., and the results are shown in FIG. 1 .
  • the cured resin sample was polished into a uniform disk, and its dielectric properties were tested. The results showed that the dielectric constant was 2.57 at 5 GHz, and the dielectric loss was 1.08 ⁇ 10 -3 ; the dielectric constant was 2.53 at 10 GHz, The dielectric loss was 1.93 ⁇ 10 -3 .
  • the DMA test results show that the glass transition temperature of cured resin P2 is 343°C.
  • P2 has good dimensional stability, and its coefficient of thermal expansion is 67.1ppm/°C in the range from room temperature to 300°C. After soaking P1 in boiling water for 72 hours, its water absorption rate was tested to be 0.19%.

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Abstract

La présente invention concerne un procédé de synthèse de verre moléculaire, et son utilisation en tant que matériau à faible constante diélectrique et haute fréquence. Spécifiquement, la présente invention concerne un monomère de verre moléculaire, qui a une structure moléculaire telle que représentée dans la formule (I) ci-dessous. Le monomère de verre moléculaire présente une excellente aptitude au traitement et peut former une résine infusible et insoluble après un traitement à haute température ; et un tel verre moléculaire présente uniquement une transition vitreuse mais aucun point de fusion lorsqu'il est chauffé, ce qui est similaire à un état amorphe. Dans la présente invention, la résine obtenue après durcissement du verre moléculaire présente une résistance élevée à la chaleur et une faible absorption d'eau, présente en particulier une excellente constante diélectrique et une excellente perte diélectrique à une fréquence élevée, et peut être largement utilisée en tant que résine à matrice à faible constante diélectrique ou matériau d'emballage dans des domaines comprenant une communication à haute fréquence, l'industrie micro-électronique, l'aérospatiale, etc.
PCT/CN2022/092261 2021-06-24 2022-05-11 Procédé de synthèse de verre moléculaire et utilisation de celui-ci en tant que matériau à faible constante diélectrique et haute fréquence WO2022267730A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442278A (en) * 1981-12-03 1984-04-10 Hughes Aircraft Company Ethynyl-substituted s-triazine derivatives, polymers thereof and process for making the same
CN110204502A (zh) * 2019-06-21 2019-09-06 陕西莱特光电材料股份有限公司 一种杂环有机光电材料及其制备方法与应用
KR20200079980A (ko) * 2018-12-26 2020-07-06 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
WO2021080333A1 (fr) * 2019-10-21 2021-04-29 덕산네오룩스 주식회사 Composé pour élément électrique organique, élément électrique organique l'utilisant, et dispositif électronique associé
CN113429358A (zh) * 2021-06-24 2021-09-24 中国科学院上海有机化学研究所 一类分子玻璃的合成方法及其作为高频低介电常数材料的应用
US20220020938A1 (en) * 2020-07-08 2022-01-20 Duk San Neolux Co., Ltd. Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4246127B2 (ja) * 2004-05-28 2009-04-02 エルジー ケーブル リミテッド 軟性金属薄膜積層フィルム及びその製造方法
CA2762434C (fr) * 2011-12-16 2019-01-15 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of National Defence Verres moleculaires avec groupes fonctionnels
CN103012298B (zh) * 2012-12-28 2015-04-01 中国科学院上海有机化学研究所 一种含三嗪环的苯并环丁烯单体、制备方法和应用
US10461269B2 (en) * 2013-12-20 2019-10-29 Molecular Glasses, Inc. Crosslinkable, /polymerizable and combinations thereof charge-transporting molecular glass mixtures, luminescent molecular glass mixtures, or combinations thereof for organic light emitting diodes and other organic electronics and photonics applications and method of making same
CN111018843B (zh) * 2019-11-01 2022-01-28 陕西莱特光电材料股份有限公司 化合物、电子元件及电子装置
KR20210069770A (ko) * 2019-12-03 2021-06-14 덕산네오룩스 주식회사 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442278A (en) * 1981-12-03 1984-04-10 Hughes Aircraft Company Ethynyl-substituted s-triazine derivatives, polymers thereof and process for making the same
KR20200079980A (ko) * 2018-12-26 2020-07-06 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
CN110204502A (zh) * 2019-06-21 2019-09-06 陕西莱特光电材料股份有限公司 一种杂环有机光电材料及其制备方法与应用
WO2021080333A1 (fr) * 2019-10-21 2021-04-29 덕산네오룩스 주식회사 Composé pour élément électrique organique, élément électrique organique l'utilisant, et dispositif électronique associé
US20220020938A1 (en) * 2020-07-08 2022-01-20 Duk San Neolux Co., Ltd. Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
CN113429358A (zh) * 2021-06-24 2021-09-24 中国科学院上海有机化学研究所 一类分子玻璃的合成方法及其作为高频低介电常数材料的应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HUANG G. ET AL.: "Thermo-crosslinkable molecular glasses towards the low k materials at high frequency", MATERIALS TODAY CHEMISTRY, vol. 24, 10 February 2022 (2022-02-10), XP093016610, ISSN: 2468-5194 *
KONDO, S. ; YAMAMOTO, T. ; MASE, M. ; MIKAMI, H. ; KUNISADA, H. ; YUKI, Y.: "Polytriazinylstyrene-supported oligo(oxyethylene)s as phase transfer catalysts", REACTIVE POLYMERS., ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM., NL, vol. 22, no. 1, 1 February 1994 (1994-02-01), NL , pages 75 - 80, XP022802955, ISSN: 0923-1137, DOI: 10.1016/0923-1137(94)90098-1 *
ZHOU JUNFENG, WANG JIAJIA, TAO YANGQING, FANG LINXUAN, SUN JING, FANG QIANG: "New Triazine-Based Polymers with Low Dielectric Constants and High Thermostability Derived from Biorenewable Anethole and Thermocrosslinkable Benzocyclobutene", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, AMERICAN CHEMICAL SOCIETY, US, vol. 6, no. 4, 2 April 2018 (2018-04-02), US , pages 5620 - 5626, XP093016612, ISSN: 2168-0485, DOI: 10.1021/acssuschemeng.8b00655 *

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