WO2022267730A1

WO2022267730A1 - Method for synthesizing molecular glass, and use thereof as high-frequency low-dielectric-constant material

Info

Publication number: WO2022267730A1
Application number: PCT/CN2022/092261
Authority: WO
Inventors: 房强; 黄港; 孙晶
Original assignee: 中国科学院上海有机化学研究所
Priority date: 2021-06-24
Filing date: 2022-05-11
Publication date: 2022-12-29
Also published as: CN113429358A; CN113429358B

Abstract

The present invention provides a method for synthesizing molecular glass, and the use thereof as a high-frequency low-dielectric-constant material. Specifically, the present invention provides a molecular glass monomer, which has a molecular structure as shown in formula (I) below. The molecular glass monomer has excellent processability and can form an infusible and insoluble resin after a high-temperature treatment; and such molecular glass only displays a glass transition but no melting point when heated, which is similar to an amorphous state. In the present invention, the resin obtained after the molecular glass is cured has high heat resistance and low water absorption, especially shows an excellent dielectric constant and dielectric loss at a high frequency, and can be widely used as a low-dielectric-constant matrix resin or packaging material in fields including high-frequency communication, the microelectronic industry, aerospace, etc.

Description

Synthesis of a Class of Molecular Glass and Its Application as a High Frequency Low Dielectric Constant Material

technical field

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.

Background technique

With the rapid development of high-frequency communication technology, 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. In the existing 5G technology, sub-6GHz and millimeter waves will be used for signal transmission. In the 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. Studies have shown that 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. There is the following relationship:

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.

In addition to low dielectric properties, 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. At present, 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.

In terms of low-dielectric thin-film substrate materials, film-forming property is a key performance parameter. At present, 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.

Contents of the invention

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.

In the first aspect of the present invention, a kind of " molecular glass " monomer is provided, and described monomer has the molecular structure shown in following formula (I):

in,

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.

In another preferred example, the halogen is fluorine.

In another preferred example, each R ₁ is the same or different, preferably the same.

In another preferred example, 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.

In another preferred example, each R ₂ is the same or different, preferably the same.

In another preferred example, R ₃ and R ₄ are the same or different, preferably the same.

In another preferred embodiment, 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.

In another preferred example, 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.

_In another preferred example, each R1 is independently selected from the following group: hydrogen, fluorine, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, triethylsilyl, triiso Propylsilyl, Tributylsilyl, Trifluoromethyl.

In another preferred embodiment, the benzocyclobutenyl is

In another preferred embodiment, the styryl is

In another preferred example, 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.

In another preferred example, each group is a specific group described in each compound of the embodiment.

In another preferred embodiment, the monomer is selected from the following group:

In another preferred example, the glass transition temperature of the monomer is 50-100°C, preferably 70-90°C.

In the second aspect of the present invention, there is provided a method for preparing the "molecular glass" monomer as described in the first aspect of the present invention, comprising the steps of:

(a) in the first inert solvent, in the presence of a base, the compound of formula II and the compound of formula III are reacted to obtain the compound of formula I;

in,

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;

In another preferred example, R ₁ , R ₂ , R ₃ , and R ₄ are as defined in the first aspect of the present invention.

In another preferred embodiment, 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.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, the method is carried out in a water-oil two-phase system.

In another preferred example, the method is carried out in the presence of a phase transfer catalyst.

In another preferred example, 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.

In another preferred embodiment, 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.

In another preferred embodiment, 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.

In another preferred example, 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.

In another preference, step (a) includes:

(a1) providing an aqueous phase: the aqueous phase includes a compound of formula III, an alkali and water;

(a2) providing an oil phase: the oil phase includes a compound of formula II, an organic solvent and a phase transfer catalyst;

(a3) adding the oil phase to the water phase, raising the temperature and stirring to react to obtain the compound of formula I.

In another preferred embodiment, 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.

In another preferred embodiment, step (a) is carried out at 0-100°C, preferably at 20-80°C, more preferably at 30-60°C.

In another preferred example, the reaction time of step (a) is 2-24h, preferably 4-16h, more preferably 6-16h.

In another preferred embodiment, after the reaction in step (a), the compound of formula I is obtained by extraction, drying, desolventization under reduced pressure, and column chromatography.

In a third aspect of the present invention, a triazine compound as shown in formula (II) is provided:

in,

R ₂ is selected from the group consisting of C3-C8 benzocycloalkenyl, C2-C6 alkenylphenyl.

In another preferred example, R ₁ and R ₂ are as defined in the first aspect of the present invention.

In another preferred example, 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 ₂ is selected from the group consisting of benzocyclobutenyl, styryl.

In another preferred embodiment, the compound is

In a fourth aspect of the present invention, there is provided a method for preparing a triazine compound as described in the third aspect of the present invention, comprising the following steps:

(1) Under the protection of an inert gas, in a second inert solvent, 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

(2) Under the protection of an inert gas, in a second inert solvent, the compound of formula A is used to perform a substitution reaction with the compound of formula C, and then with the compound of formula B to perform a substitution reaction to obtain the compound of formula II;

in,

X ₁ and X ₂ are each independently halogen, preferably Cl or Br.

In another preferred example, said step (1) includes the following steps:

(a1) Under the protection of an inert gas, the intermediate 1 is obtained by performing a substitution reaction with a compound of formula A and a compound of formula B;

(b1) In a second inert solvent, the intermediate 1 is subjected to a substitution reaction with the compound of formula C to obtain the compound of formula II;

Wherein, R ₁ and R ₂ are as defined in the first aspect of the present invention.

In another preferred embodiment, the inert gas is selected from the group consisting of nitrogen and argon.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, step (a1) is carried out at -20-10°C, preferably -10-5°C, more preferably -5-0°C.

In another preferred example, the reaction time of step (a1) is 10-30h, preferably 15-25h.

In another preferred example, 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.

In another preferred embodiment, 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.

In another preferred embodiment, the compound of formula C is selected from the group consisting of 4-benzocyclobutenylmagnesium bromide, 4-styrylmagnesium bromide, or combinations thereof.

In another preferred example, 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.

In another preferred example, the second inert solvent is selected from the group consisting of chloroform, toluene, acetone, tetrahydrofuran, dioxane, or combinations thereof, preferably tetrahydrofuran.

In another preferred example, step (b1) is carried out at 5-60°C, preferably 10-50°C, more preferably 10-45°C.

In another preferred example, the reaction time of step (b1) is 2-15h, preferably 5-10h, more preferably 6-8h.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, 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.

In another preferred embodiment, after the reaction in step (b1), the solvent is removed under reduced pressure, and the compound of formula II is obtained by column chromatography.

In another preference, said step (2) includes the following steps:

(a2) In a second inert solvent, carry out a Grignard reaction with a compound of formula A and a compound of formula C to obtain intermediate 2;

(b2) Under the protection of an inert gas, the intermediate 2 is subjected to a Grignard reaction with the compound of formula B to obtain the compound of formula II;

In another preferred example, the 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).

In another preference, the preparation method of the compound of formula III comprises the following steps:

(1) In a third inert solvent, in the presence of a base, the compound of formula D and the compound of formula E are hydrolyzed to obtain intermediate 3;

(2) Under the protection of an inert gas, intermediate 3 is heated to carry out a rearrangement reaction to obtain a compound of formula III;

Wherein, 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.

In another preferred example, R ₃ and R ₄ are as defined in the first aspect of the present invention.

In another preferred example, the compound of formula D is a bisphenol compound substituted by R ₃ and R ₄ , preferably bisphenol A or bisphenol AF.

In another preferred example, the molar ratio of the compound of formula D to the compound of formula E is 3-5:1.

In another preferred example, the third inert solvent is selected from the group consisting of chloroform, toluene, acetone, tetrahydrofuran, dioxane, or combinations thereof, preferably acetone.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, step (1) is carried out at 40-100°C, preferably at 50-80°C, more preferably at 60-70°C.

In another preferred example, the reaction time of step (1) is 6-48h, preferably 12-24h.

In another preferred example, the heating temperature in step (2) is 160-250°C.

In another preferred example, the reaction time of the reaction is 6-48h, preferably 9-24h.

In another preferred example, after the reaction is completed, the compound of formula III is obtained by rectifying under reduced pressure and separated by column chromatography.

In the fifth aspect of the present invention, a cured product is provided, the cured product is formed by cross-linking reaction of cured raw materials;

Wherein, the curing raw material includes the "molecular glass" monomer described in the first aspect of the present invention.

In another preferred embodiment, the cured product is formed by cross-linking the cured raw material through a D-A reaction between double bonds and cycloolefins.

In another preferred example, 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.

In another preferred example, 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 .

In another preferred example, the curing raw material also includes a thermally curable monomer comprising an R2 group in the structure _;

in,

R ₂ is selected from the group consisting of C3-C8 benzocycloalkenyl, C2-C6 alkenylphenyl, preferably benzocyclobutenyl, styryl.

_In another preferred example, 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.

In another preferred embodiment, the curing raw material further includes thermally curable low-dielectric polymers, such as low-dielectric polyimide, polyphenylene ether, polytetrafluoroethylene, and the like.

In another preferred example, the mole fraction of "molecular glass" monomer in the curing raw material is 10%-100%, preferably 30%-100%, more preferably 50%-100%.

In another preferred example, the curing raw material is the "molecular glass" monomer described in the first aspect of the present invention.

In another preferred example, the cured product is obtained by cross-linking the "molecular glass" monomer described in the first aspect of the present invention.

In another preferred embodiment, the cured product is a three-dimensional structure obtained by a cross-linking reaction, which is a polymer.

In another preferred example, the cured product is a resin.

In another preferred example, the degree of crosslinking of the cured product is 50%-100%, preferably 70%-100%.

In another preferred example, 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.

In another preference, the cured product has one or more of the following characteristics:

(i) glass transition temperature is 250～500 ℃, preferably 300～400 ℃, more preferably 330～250 ℃;

(ii) a dielectric constant of 2.0 to 3.0 (in the range of 5-10 GHz), preferably 2.4 to 2.7, more preferably 2.5 to 2.7;

(iii) 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 ;

(iv) The coefficient of thermal expansion is 40-80ppm/°C (in the range of room temperature to 300°C), preferably 60-70ppm/°C;

(v) The water absorption rate is 0.15-0.4% (after soaking in boiling water for 24-96 hours).

In the sixth aspect of the present invention, there is provided a method for preparing a cured product according to the fifth aspect of the present invention, the method comprising the steps of: heating and curing the curing raw material to obtain a cured product;

In another preferred example, the curing raw material is as described in the fifth aspect of the present invention.

In another preferred embodiment, 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.

In another preferred example, 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 .

In another preferred example, the method for preparing the cured product is a method for curing raw materials.

In another preferred example, the curing is cross-linking and curing by heating (ie heat curing).

In another preferred embodiment, 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.

In another preferred example, the heat curing is carried out at 100-350°C, preferably 150-300°C.

In another preferred example, the heat curing is temperature programmed curing.

In another preferred example, 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.

In another preferred example, 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.

In another preferred example, the heating and curing temperature is determined by the DSC curve of the curing raw material.

In another preferred example, the heating and curing time is determined by the structure, quality and shape of the curing raw material.

In another preferred example, 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.

In the seventh aspect of the present invention, a product is provided, 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;

Or 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.

In another preferred example, 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.

In another preferred embodiment, 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.

In another preferred example, 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.

In another preferred embodiment, the forming is carried out by a forming process selected from the following group: pouring, solution spin coating, or solution drop coating.

In another preferred example, 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;

Wherein, the prepolymer is an oligomer obtained by dissolving curing raw materials in a fourth inert solvent and heating and crosslinking.

In another preferred example, the prepolymer still maintains good solubility in the solution and has good processability.

In another preferred example, the degree of crosslinking of the prepolymer is 0.1%-50%, preferably 5%-30%.

In the eighth aspect of the present invention, there is provided a product as described in the seventh aspect of the present invention, 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.

It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described in the following (such as embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, we will not repeat them here.

Description of drawings

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).

detailed description

After extensive and in-depth research, 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. In addition, 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℃), low thermal expansion coefficient (25-300℃, CTE as low as 63.0ppm/℃), 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.

the term

In the present invention, unless otherwise specified, the terms used have the usual meanings known to those skilled in the art.

The terms "'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.

The term "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.

The term "benzocyclobutenyl" refers to a group formed by losing a hydrogen atom on the benzene ring of benzocyclobutene, for example

or similar groups.

The term "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.

The term "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.

In the present invention, the term "halogen" refers to F, Cl, Br or I.

In the present invention, the term "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.

In the present invention, the term "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.

In the present invention, the term "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.

In the present invention, the term "aromatic ring" or "aryl" has the same meaning, preferably "C6-C10 aryl". The term "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.

In the present invention, the term "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. Unless otherwise specified, 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. Those skilled in the art will appreciate that combinations of 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.

In the present invention, the term 1-6 refers to 1, 2, 3, 4, 5 or 6. Other similar terms have similar meanings.

The term "plurality" refers to 1, 2, 3, 4, 5 or 6.

molecular glass

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.

In the process of molecular design of molecular glass, 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. After that, 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. In addition, 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. In general, 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.

Molecular vitrified resin

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 main advantages of the present invention include:

1) The preparation process of the "molecular glass" monomer described in the present invention is simple. Starting from simple and easy-to-obtain raw materials, a triazine intermediate can be obtained through a simple Grignard reaction, and then obtained by direct hydrolysis polymerization. A group of "molecular glass" monomers, the synthesis steps are simple, the conditions are mild, and the yield is high.

2) 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;

3) 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.

4) 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℃), low thermal expansion coefficient (25-300℃, CTE as low as 63.0ppm/℃) 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 ).

5) 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.

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. For the experimental methods not indicated in the following examples, the specific conditions are usually in accordance with conventional conditions, for example, in accordance with the conditions suggested by the manufacturer. Percentages and parts are by weight unless otherwise indicated.

General Test Method

DMA testing (i.e. dynamic thermomechanical analysis)

Dynamic thermomechanical analysis (DMA) was tested by a DMA/Q800 instrument under a nitrogen atmosphere with a heating rate of 5 °C/min.

Dielectric performance test

The dielectric constant and dielectric loss were measured by a separate dielectric resonator (QWED) at room temperature at a frequency of 5/10 GHz.

Water absorption test

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

Under the protection of nitrogen gas, add 180mmol of magnesium chips, 100mL of tetrahydrofuran and a grain of iodine (about 40mg) to a 250mL dry three-necked flask, then slowly add 120mmol of 4-bromotoluene dropwise to keep the solution slightly boiling, and stir at reflux for 1h to obtain 4 - Methylphenyl Grignard reagent.

Take another 500mL dry three-necked flask, add 80mmol 2,4,6-trichloro-1,3,5-triazine under nitrogen protection, add 120mmol 4-methylbenzene Grignard reagent dropwise, and stir at -5°C Reacted for 19 hours. Quenched with ammonium chloride, extracted with ethyl acetate, concentrated to remove the solvent and followed by column chromatography to obtain 16.97 g of white solid compound 1 with a yield of 88%. ¹ H NMR (CDCl ₃ , 400MHz), δ (ppm) 8.37 (d, J = 8.1Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 2.44 (s, 3H). ¹³ C NMR (CDCl ₃ ,126MHz), δ(ppm)174.74,171.85,146.07,129.99,129.86,21.93.

Add 68mmol of compound 1 and 200mL of anhydrous tetrahydrofuran to a 500mL dry three-necked flask, and add dropwise 102mmol of preformed (preparation method is the same as the aforementioned 4-methylbenzene Grignard reagent) dissolved in 150mL of anhydrous tetrahydrofuran 4-bromo Benzocyclobutene Grignard reagent. After the dropwise addition was completed, the mixture was stirred at room temperature for 7.5 hours. The solvent was removed under reduced pressure, and the white disubstituted 1,3,5-triazine intermediate S1 was obtained by column chromatography with a yield of 73%.

¹ H NMR (CDCl ₃ , 400MHz), δ(ppm) 8.52(d, J=7.2Hz, 1H), 8.49(d, J=8.1Hz, 2H), 8.28(s, 1H), 7.32(d, J =8.1Hz, 2H), 7.20(d, J=7.8Hz, 1H), 3.26(s, 4H), 2.45(s, 3H).

¹³ C NMR (CDCl ₃ , 126MHz), δ (ppm) 173.92, 173.15, 171.87, 152.62, 146.36, 144.33, 133.24, 131.80, 129.56, 129.38, 128.77, 123.38, 122.87, 30.07, 219.82.

Embodiment 2. Synthesis of Molecular Glass Monomer M1

Take a 500 mL single-necked flask, add 13.2 mmol of intermediate S2, 48.0 mmol of NaOH and 80 mL of H ₂ O, and stir at room temperature for 0.5 h. Continue to add 120 mL of CHCl ₃ , 24 mmol of intermediate S1 and 0.13 mmol of phase transfer catalyst cetyltrimethylammonium bromide. Raise the temperature to 60°C and react for 14h under vigorous stirring. After stopping the reaction, it was extracted with dichloromethane, dried, and the solvent was removed under reduced pressure. Column chromatography gave 7.70 g of white amorphous "molecular glass" monomer M1, yield: 75%.

¹ H NMR (500MHz, CDCl ₃ ) δ8.33(dd, J=11.6, 8.3Hz, 6H), 8.10(s, 2H), 7.19(dd, J=15.0, 5.0Hz, 6H), 7.13(dd, J=8.4,2.0Hz,2H),7.06(dd,J=16.1,8.1Hz,4H),5.80(ddt,J=13.0,10.0,6.5Hz,2H),4.99–4.76(m,4H),3.31 (d,J=6.3Hz,4H),3.11(s,8H),2.31(s,6H),1.72(s,6H).

¹³ C NMR(CDCl ₃ ,126MHz),δ(ppm)174.55,173.79,171.83,151.70,148.46,148.29,146.05,143.42,136.08,134.30,132.84,131.51,129.33,129.08,128.68,128.38,126.08,123.14, 122.61, 121.88, 116.19, 42.71, 34.77, 31.09, 29.94, 29.39, 21.74.

Embodiment 3. the synthesis of intermediate S2'

Take 250mL sealed tube, add 50mL acetone, 25mmol K ₂ CO ₃ , 10mmol bisphenol AF, first stir at room temperature for 30min, continue to add S2, heat up to 70°C for overnight reaction. After the reaction was stopped, the insoluble impurities were removed by suction filtration, and the solvent was spin-dried to obtain 4.11 g of the diallyl-substituted target intermediate as a colorless transparent liquid with a yield of 98.9%. The obtained intermediate was directly placed into a 50 mL single-necked flask, nitrogen was replaced 3 times, and reacted at 210° C. for 9 h. After the reaction was stopped, column chromatography was separated to obtain 3.771 g of light yellow liquid, yield: 91.7%.

¹ H NMR (CDCl ₃ , 400MHz) δ(ppm) δ7.16(d, J=8.8Hz, 2H), 7.11(s, 2H), 6.80(d, J=8.5Hz, 2H), 5.97(m, 2H), 5.55(s, 2H, OH), 5.12(dd, J＝12.0, 10.3Hz, 4H), 3.38(d, J＝6.2Hz, 4H). ¹⁹ F NMR (CDCl ₃ , 376MHz) δ (ppm )-63.96(s,6F).

Example 4. Synthesis of Molecular Glass Monomer M2

Take a 500mL single-necked bottle, add 7.2mmol monomer S2', 26.0mmol NaOH and 60mL H ₂ O, and stir at room temperature for 0.5h. Continue to add 80 mL of CHCl ₃ , 13.0 mmol of monomer S1 and 0.07 mmol of phase transfer catalyst cetyltrimethylammonium bromide. Raise the temperature to 60°C and react for 12.5h under vigorous stirring. After the reaction was stopped, it was extracted with dichloromethane, dried, and the solvent was removed under reduced pressure. Column chromatography gave 4.54 g of white amorphous "molecular glass" monomer M2, yield: 73%.

¹ H NMR (CDCl ₃ , 400MHz), δ (ppm) 8.41–8.29 (m, 6H), 8.11 (s, 2H), 7.36 (d, J=7.6Hz, 4H), 7.25–7.16 (m, 6H) ,7.08(d,J=7.7Hz,2H),5.76(ddt,J=16.6,10.0,6.4Hz,2H),4.90–4.84(m,4H),3.33(d,J=6.4Hz,4H), 3.15(s,8H),2.35(s,6H).

¹³ C NMR(CDCl ₃ ,126MHz),δ174.67,173.92,171.57,151.93,151.11,146.15,143.66,135.17,134.14,132.68,132.64,132.57,130.97,129.39,129.12,128.42,127.74-120.89(q),123.16 ,122.67,122.49,116.84,77.34,77.08,76.83,67.49-57.87(m),34.46,29.97,29.38,21.73.

Example 5. Research on the curing of molecular glass monomer M1 and its corresponding resin properties

Take the target monomer M1 prepared in Example 2 and put it into a tube furnace. 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. The results show that the dielectric constant is 2.70 at 5 GHz, the dielectric loss is 1.82×10 ^-3 , and the dielectric constant is 2.67 at 10 GHz. The electrical loss is 2.22×10 ^-3 . As shown in Figure 2, DMA (Dynamic Thermomechanical Analysis) test results show that the glass transition temperature of cured resin P1 is 339°C. As shown in Figure 3, it is found through the CTE (coefficient of thermal expansion) test that P1 has good dimensional stability, and the thermal expansion coefficient is 62.6ppm/°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 0.36%.

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 . As shown in Figure 2, the DMA test results show that the glass transition temperature of cured resin P2 is 343°C. As shown in Figure 3, it is found through CTE testing that 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%.

All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims

A kind of " molecular glass " monomer, is characterized in that, described monomer has the molecular structure shown in following formula (I):

in,

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.
"Molecular glass" monomer as claimed in claim 1, characterized in that,

Each R is independently selected from the group consisting of hydrogen, halogen, C1 -C6 alkyl, C1-C6 haloalkyl, 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 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-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.
The preparation method of "molecular glass" monomer as claimed in claim 1, is characterized in that, comprises the steps:

(a) in the first inert solvent, in the presence of a base, the compound of formula II and the compound of formula III are reacted to obtain the compound of formula I;

in,

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.
The preparation method according to claim 3, wherein 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, trichloromethane, dichloroethane alkanes, toluene, xylene, or combinations thereof.
A triazine compound as shown in formula (II):

in,

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.
The preparation method of triazine compound as claimed in claim 5, is characterized in that, comprises the following steps:

(1) Under the protection of an inert gas, in a second inert solvent, 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

(2) Under the protection of an inert gas, in a second inert solvent, the compound of formula A is used to perform a substitution reaction with the compound of formula C, and then with the compound of formula B to perform a substitution reaction to obtain the compound of formula II;

in,

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.
A cured product, characterized in that, the cured product is formed by curing raw materials through a crosslinking reaction;

Wherein, the solidified raw material comprises the "molecular glass" monomer as claimed in claim 1.
The method for preparing a cured product according to claim 7, wherein the method comprises the steps of: heating and curing the curing raw material to obtain a cured product;

Wherein, the solidified raw material comprises the "molecular glass" monomer as claimed in claim 1.
A product, characterized in that the product contains the cured product as claimed in claim 7, the "molecular glass" monomer as claimed in claim 1;

Or the article is prepared with the cured product as claimed in claim 7, the "molecular glass" monomer as claimed in claim 1.
The product according to claim 9, wherein 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 material, high frequency low dielectric electric constant material.