CN103865066B - Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer - Google Patents

Abstract

The present invention relates to the low dielectric constant polymer containing hexafluorocyclobutyl ether and organosiloxane and its preparation and application, specifically, the present invention provides a polymer as shown in formula I for heat curing The resulting polymers, their preparation and use. The polymer has good electrical performance and heat resistance, and the preparation method is simple, and is suitable for the electrical and electronic industry as an insulating coating layer and packaging material for electronic components.

Description

Low dielectric constant polymer containing hexafluorocyclobutyl ether and organosiloxane and its preparation and application

technical field

The invention belongs to the technical field of high-performance polymer production, in particular, the invention relates to a low dielectric constant polymer containing hexafluorocyclobutyl ether and siloxane with excellent mechanical properties, low water absorption and low dielectric constant , and its preparation method and application.

Background technique

Traditionally, silicon dioxide or organic silicon-based materials are used as interlayer low dielectric materials in integrated circuits. Although these materials have very high thermal stability and thermomechanical properties, their dielectric constants are often higher than 3.0, which cannot meet the requirements of high-frequency communication equipment. Polyimide materials are widely used as a substitute for silicon dioxide because of their good heat resistance and the possibility of obtaining thin films with a lower dielectric constant by forming holes. However, the glass transition temperature of ordinary polyimide is often lower than the processing temperature of integrated circuit boards, and the material is easily arranged along the metal or silicon surface during film formation, so that polyimide has a low dielectric Electrical materials exhibit anisotropy, including anisotropy in thermal conductivity, shear strength, and dielectric properties. Therefore, industrial departments and research institutes have further developed many organic polymer-based low-dielectric materials. However, these materials often have insufficient thermal stability and poor surface adhesion to metals or silicon. With the development of the microelectronics industry, the manufacturing of 90-nanometer chips based on copper interconnection technology has put forward many demands on the material industry, and the pure silicon-containing and organic polymers mentioned above will gradually be eliminated. The most pressing problem facing people is the need to develop materials with both low dielectric constant and high heat resistance.

Polyhexafluorocyclobutyl aryl ether materials have been studied since the 1990s because of their excellent heat resistance and photoelectric properties. So far, they have been fully exploited as organic photoconductive materials due to their high transmission efficiency and minimal light loss (see Macromolecules 2004, 37, 5724 and Macromolecules 2005, 38, 8278). On the other hand, because the C-F bond has a small polarizability, a thermosetting resin containing a hexafluorocyclobutyl aryl ether functional group in the main chain is prepared by curing at a high temperature using a trifunctional trifluorovinyl ether structure as a prepolymer Has been developed and used as a low dielectric constant material (see Mat. Res. Soc. Symp. Proc. 1997, 443, 177). In recent years, perfluorocyclobutane aryl ether (polyperfluorocyclobutane, PFCB) polymers derived from tetrafluoroethylene have received great attention because of their relatively low cost and excellent electrical properties. And low moisture absorption (see WO9015043). However, low-dielectric materials based entirely on PFCB organic framework structures suffer from insufficient thermal stability and bonding performance. Therefore, it is necessary to work on improving and eliminating these defects.

Contents of the invention

The purpose of the present invention is to provide a low dielectric material with PFCB organic framework structure with improved thermal stability and bonding performance.

The first aspect of the present invention provides a polymer as shown in formula I:

In the formula, n≥2; preferably, n=5-100; more preferably, n=10-20.

In another preferred embodiment, the polymer of formula I is in a liquid state, preferably a colorless viscous liquid.

In another preferred example, the number average molecular weight of the polymer is 2,300-4,600.

In another preferred example, the weight average molecular weight of the polymer is 4,300-8,600.

In another preferred example, the polymer of formula I can be cured by heating, preferably, the curing temperature of the polymer of formula I is 150°C-250°C.

The second aspect of the present invention provides a method for preparing the polymer of formula I as described in the first aspect of the present invention, said method comprising the steps of: in an inert solvent, using trifluoroethylene as shown in the following formula II The organosilicon monomer of the base ether unit is subjected to a hydrolysis polymerization reaction to obtain a polymer of formula I;

Wherein, R is selected from the following group: C1-C4 alkyl; n is as defined above.

In another preferred embodiment, the hydrolytic polymerization reaction is carried out in a solvent selected from the following group: benzene, toluene, xylene, or a combination thereof.

In another preferred example, the reaction temperature of the hydrolytic polymerization reaction is 0-100°C.

In another preferred example, the hydrolytic polymerization reaction time is 5-36 hours.

In another preferred example, the hydrolytic polymerization reaction time is 12-36 hours.

In another preferred example, the hydrolysis polymerization reaction is carried out in the presence of an acidic catalyst and/or water.

In another preferred embodiment, the acidic catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, formic acid, or combinations thereof.

In another preferred example, in the hydrolysis polymerization reaction, the molar ratio of water, acidic catalyst and organosilicon monomer represented by formula II is 50-100:1-10:1-10.

In another preferred example, the organosilicon monomer represented by the formula II is prepared by the following steps:

(1) In a polar aprotic solvent, in the presence of a basic catalyst, react with p-halogenated phenol and tetrafluorodibromoethane at room temperature to prepare 4-(2-bromo-1,1,2, 2-tetrafluoroethoxy)-1-halobenzene;

(2) In a polar aprotic solvent, the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halogenated benzene is eliminated to obtain 4-(1,2,2-Trifluoroethyleneoxy)-1-halobenzene;

(3) In a polar aprotic solvent, react methyltrialkoxysilane with 4-(1,2,2-trifluoroethyleneoxy)-1-halogenated benzene to obtain the formula II Silicone monomer;

In the above formulas, X is halogen; R is selected from the following group: C1-C4 alkyl.

In another preferred example, in the step (1), the basic catalyst is selected from the group consisting of potassium carbonate, potassium hydroxide, or a combination thereof.

In another preferred example, in the step (1), the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, DMSO, or a combination thereof.

In another preferred example, in the step (1), the p-halogenated phenol is selected from the group consisting of p-bromophenol, p-chlorophenol, or a combination thereof.

In another preferred example, in the step (1), the reaction time is 5-30 hours.

In another preferred example, in the step (1), the molar ratio of p-halogenated phenol to tetrafluorodibromoethane is 1:1-10.

In another preferred example, in the step (2), the polar aprotic solvent is acetonitrile.

In another preferred example, in the step (2), the elimination reaction is carried out in the presence of zinc powder.

In another preferred example, in the step (2), the reaction time is 5-30 hours.

In another preferred example, in the step (2), the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halogenated benzene and zinc The molar ratio of powder is 1:1~5.

In another preferred example, in the step (3), the polar aprotic solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, or a combination thereof.

In another preferred example, in the step (3), the reaction is carried out in the presence of magnesium chips.

In another preferred example, in the step (3), the alkoxy group is a C1-C4 alkoxy group, preferably, the alkoxy group is selected from the group consisting of methoxy or Ethoxy.

In another preferred example, in the step (3), the 4-(1,2,2-trifluoroethyleneoxy)-1-halobenzene is added in the following way: after being prepared as a tetrahydrofuran solution Add dropwise.

In another preferred example, in the step (3), the reaction time is 12-36 hours.

In another preferred example, in the step (3), the reaction temperature is 0-50°C.

The third aspect of the present invention provides a use of the polymer of formula I according to the first aspect of the present invention for heat curing to prepare a cured polymer.

In another preferred example, the heating and curing temperature is 150°C to 250°C.

The fourth aspect of the present invention provides a polymer, which is prepared by curing the polymer described in formula I: preferably, the curing is heat curing.

In another preferred example, the polymer has a structure as shown in formula III:

In the formula, m is a positive integer, and m≤n.

In another preferred example, the polymer (final cured product) Si-PFCB has a cross-linked network structure.

In another preferred example, the polymer has one or more of the following characteristics:

The dielectric constant of the polymer is ≤2.5, preferably ≤2.4 (measured at 30MHz);

Under nitrogen atmosphere, the 5% thermal decomposition temperature of the polymer is ≥450°C, preferably ≥470°C;

The hardness of the polymer is ≥0.35GPa, preferably ≥0.38GPa;

The Young's modulus of the polymer is ≥8.00GPa, preferably ≥9.00GPa, more preferably ≥10.00GPa;

The bonding strength between the polymer and the silicon wafer is ≥4.5GPa, preferably ≥4.8GPa, more preferably ≥4.90GPa.

The fifth aspect of the present invention provides a method for preparing the polymer as described in the fourth aspect of the present invention, the polymer is prepared by the following method: heating the polymer shown in formula I, so as to obtain the polymer according to the present invention The polymer described in the fourth aspect.

In another preferred example, the heating temperature ranges from 150°C to 250°C.

The sixth aspect of the present invention provides a product, which contains the polymer of formula I as described in the first aspect of the present invention or the polymer as described in the fourth aspect of the present invention, or the product is used as Prepared from the polymer of formula I described in the first aspect of the present invention or the polymer described in the fourth aspect of the present invention.

In another preferred embodiment, the product is selected from the group consisting of low dielectric constant materials, insulating materials for covering metal wires, polymer sheets, and polymer films.

In another preferred embodiment, the product is a heavily doped silicon wafer - the polymer film as described in the fourth aspect of the present invention.

In another preferred example, the product is a glass fiber-polymer composite material as described in the fourth aspect of the present invention.

In another preferred example, the product is a printed circuit board.

In another preferred embodiment, the product is a polymer sheet or polymer film containing the polymer described in the fourth aspect of the present invention, and the product is prepared by the following method:

Use the polymer of formula I described in the first aspect of the present invention to perform room temperature molding to obtain a sheet containing the polymer of formula I; or dissolve the polymer of formula I with an organic solvent and form a film to obtain a film containing the polymer of formula I ;

The above-mentioned polymer sheet or polymer film is heat-cured to obtain a polymer sheet or polymer film containing the polymer as described in the fourth aspect of the present invention.

In another preferred example, the film forming process is spin coating film forming or drop coating film forming.

In another preferred example, the organic solvent is toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N-di Methylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or combinations thereof.

The seventh aspect of the present invention provides an organosilicon monomer represented by the following formula II:

Wherein, R is selected from the following group: C1-C4 alkyl.

The eighth aspect of the present invention provides a method for preparing the organosilicon monomer as described in the seventh aspect of the present invention, which is prepared by the following steps:

(1) In a polar aprotic solvent, in the presence of a basic catalyst, react with p-halogenated phenol and tetrafluorodibromoethane at room temperature to prepare 4-(2-bromo-1,1,2, 2-tetrafluoroethoxy)-1-halobenzene;

(2) In a polar aprotic solvent, the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halogenated benzene is eliminated to obtain 4-(1,2,2-Trifluoroethyleneoxy)-1-halobenzene;

(3) In a polar aprotic solvent, react methyltrialkoxysilane with 4-(1,2,2-trifluoroethyleneoxy)-1-halogenated benzene to obtain the formula II Silicone monomer;

In the above formulas, X is halogen; R is selected from the following group: C1-C4 alkyl.

In another preferred example, in the step (1), the basic catalyst is selected from the group consisting of potassium carbonate, potassium hydroxide, or a combination thereof.

In another preferred example, in the step (1), the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, DMSO, or a combination thereof.

In another preferred example, in the step (1), the p-halogenated phenol is selected from the group consisting of p-bromophenol, p-chlorophenol, or a combination thereof.

In another preferred example, in the step (1), the reaction time is 5-30 hours.

In another preferred example, in the step (1), the molar ratio of p-halogenated phenol to tetrafluorodibromoethane is 1:1-10.

In another preferred example, in the step (2), the polar aprotic solvent is acetonitrile.

In another preferred example, in the step (2), the elimination reaction is carried out in the presence of zinc powder.

In another preferred example, in the step (2), the reaction time is 5-30 hours.

In another preferred example, in the step (2), the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halogenated benzene and zinc The molar ratio of powder is 1:1~5.

In another preferred example, in the step (3), the polar aprotic solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, or a combination thereof.

In another preferred example, in the step (3), the reaction is carried out in the presence of magnesium chips.

In another preferred example, in the step (3), the alkoxy group is a C1-C4 alkoxy group, preferably, the alkoxy group is selected from the group consisting of methoxy or Ethoxy.

In another preferred example, in the step (3), the 4-(1,2,2-trifluoroethyleneoxy)-1-halobenzene is added in the following way: after being prepared as a tetrahydrofuran solution Add dropwise.

In another preferred example, in the step (3), the reaction time is 12-36 hours.

In another preferred example, in the step (3), the reaction temperature is 0-50°C.

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.

detailed description

After long-term and in-depth research, the inventors found that after the organosiloxane containing trifluorovinyl ether functional group is hydrolyzed, the obtained prepolymer is directly cured at high temperature, and a novel organosiloxane material can be obtained . The material has good electrical properties, thermal stability and bonding performance, and is suitable as a high-performance coating and packaging material with high heat resistance and low dielectric constant, and is used in the microelectronics industry, aerospace and national defense and other fields. Based on the above findings, the inventors have accomplished the present invention.

the term

As used herein, the terms "cured product of polymer of formula II", "Si-PFCB polymer of the present invention" or "low dielectric constant polymer containing hexafluorocyclobutyl ether and organosiloxane" all refer to Formula II polymer of the present invention carries out the polymer prepared by heat curing, and a kind of preferred structure is as shown in formula III:

Unless otherwise specified, the term "halo" means that one or more hydrogen atoms on a group are replaced by halogen atoms, wherein the halogen atoms are selected from the group consisting of fluorine, chlorine, bromine, and iodine.

The term "C1-C4 alkyl" refers to a straight chain or branched chain alkyl group with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or similar groups.

The term "C1-C4 alkoxy" refers to a straight-chain or branched alkoxy group having 1-4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso Butoxy, sec-butoxy, tert-butoxy, or the like.

Fluorinated silicone prepolymer

The present invention provides a prepolymer that can be used to prepare low dielectric constant polymers containing hexafluorocyclobutyl ether and organosiloxane, and the prepolymer is shown in formula I:

In the formula, n≥2; preferably, n=5-100; more preferably, n=10-20.

In another preferred example, the number average molecular weight of the polymer is 2,300-4,600.

In another preferred example, the weight average molecular weight of the polymer is 4,300-8,600.

In a preferred example of the present invention, the polymer of formula I can be prepared by hydrolytic polymerization of monomers, for example:

In an inert solvent, the organosilicon monomer containing trifluorovinyl ether unit shown in the following formula II is used for hydrolysis polymerization to obtain the polymer of formula I;

Wherein, R is selected from the following group: C1-C4 alkyl; n≥2; preferably, n=5-100; more preferably, n=10-20.

In another preferred embodiment, the hydrolytic polymerization reaction is carried out in a solvent selected from the following group: benzene, toluene, xylene, or a combination thereof.

The reaction temperature of the hydrolysis polymerization reaction is not particularly limited, for example, it can be carried out at the reflux temperature of the solvent, or at the boiling point of ROH. In a preferred example of the present invention, the reaction temperature is 0-100°C, preferably 4-95°C.

In another preferred example, the hydrolytic polymerization reaction time is 5-20 hours.

The hydrolytic polymerization reaction can be carried out in the presence of a catalyst, for example, in a preferred embodiment of the present invention, the reaction is carried out in the presence of an acidic catalyst and/or water. Wherein, the acidic catalyst includes (but is not limited to) an acid selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, formic acid, or a combination thereof.

In another preferred example, in the hydrolysis polymerization reaction, the molar ratio of water, acidic catalyst and organosilicon monomer represented by formula II is 50-100:5-10:1.

The organosilicon monomer represented by the formula II can be prepared by conventional methods in the art, for example, can be prepared by the following steps:

(1) In a polar aprotic solvent, in the presence of a basic catalyst, react with p-halogenated phenol and tetrafluorodibromoethane at room temperature to prepare 4-(2-bromo-1,1,2, 2-tetrafluoroethoxy)-1-halobenzene;

In another preferred example, in the step (1), the basic catalyst is selected from the group consisting of potassium carbonate, potassium hydroxide, or a combination thereof.

In another preferred example, in the step (1), the polar aprotic solvent is selected from the group consisting of N-methylpyrrolidone, DMSO, or a combination thereof.

In another preferred example, in the step (1), the p-halogenated phenol is selected from the group consisting of p-bromophenol, p-chlorophenol, or a combination thereof.

The reaction time of the step (1) is not particularly limited, and the reaction end point can be determined by TLC method. In a preferred example of the present invention, the reaction time is 10-30 hours.

In another preferred example, in the step (1), the molar ratio of p-halogenated phenol to tetrafluorodibromoethane is 1:1-10.

(2) In a polar aprotic solvent, the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halogenated benzene is eliminated to obtain 4-(1,2,2-Trifluoroethyleneoxy)-1-halobenzene;

Wherein, the polar aprotic solvent is not particularly limited, preferably acetonitrile.

The elimination reaction can be carried out under optional catalytic conditions of a catalyst, or under any suitable reaction conditions, for example, it can be carried out under the action of zinc powder.

The reaction time of the step (2) is not particularly limited, and the reaction end point can be determined by TLC method. In a preferred example of the present invention, the reaction time is 5-30 hours.

In another preferred example, in the step (2), the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halogenated benzene and zinc The molar ratio of powder is 1:1~5.

(3) In a polar aprotic solvent, react methyltrialkoxysilane with 4-(1,2,2-trifluoroethyleneoxy)-1-halogenated benzene to obtain the formula II of silicone monomers.

In another preferred example, in the step (3), the polar aprotic solvent is selected from the group consisting of tetrahydrofuran, diethyl ether, or a combination thereof.

In another preferred example, in the step (3), the reaction is carried out in the presence of magnesium chips.

In another preferred example, in the step (3), the alkoxy group is a C1-C4 alkoxy group, preferably, the alkoxy group is selected from the group consisting of methoxy or Ethoxy.

In another preferred example, in the step (3), the 4-(1,2,2-trifluoroethyleneoxy)-1-halobenzene is added in the following way: after being prepared as a tetrahydrofuran solution Add dropwise.

In another preferred example, in the step (3), the reaction time is 12-36 hours.

In another preferred example, in the step (3), the reaction temperature is 0-50°C.

In another preferred example, in the step (3), the 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-1-halogenated benzene and zinc The molar ratio of powder is 1:1~5.

The (or prepolymer) of described formula I polymer can be heat-cured, thereby prepare the low dielectric constant polymer containing hexafluorocyclobutyl ether and organosiloxane, a kind of preferred described polymer is A polymer as shown in formula III.

Low dielectric constant polymer containing hexafluorocyclobutyl ether and organosiloxane

Based on the high heat resistance, easy processability and good adhesion to silicon wafers of silicone, and the low dielectric properties of hexafluorocyclobutyl aryl ether, if the two are combined, theoretically good heat resistance can be obtained , Low dielectric constant material with good mechanical properties. The present invention is just based on the research status of the above-mentioned low dielectric materials, proceeds from the theory of molecular design, combines hexafluorocyclobutyl aryl ether and organosiloxane to obtain a thermosetting material.

Specifically, the present invention provides a polymer (that is, the Si-PFCB polymer of the present invention) prepared by heat-curing the polymer of formula I above. A preferred structure of the polymer is shown in formula III:

In the formula, m is a positive integer, and m≤n.

In a preferred embodiment of the present invention, the Si-PFCB polymer of the present invention has a cross-linked network structure.

In another preferred example, the polymer has one or more of the following characteristics:

The dielectric constant of the polymer is ≤2.5, preferably ≤2.4 (measured at 30MHz);

Under nitrogen atmosphere, the 5% thermal decomposition temperature of the polymer is ≥450°C, preferably ≥470°C;

The hardness of the polymer is ≥0.35GPa, preferably ≥0.38GPa;

The Young's modulus of the polymer is ≥8.00GPa, preferably ≥9.00GPa, more preferably ≥10.00GPa;

The bonding strength between the polymer and the silicon wafer is ≥4.5GPa, preferably ≥4.8GPa, more preferably ≥4.90GPa.

In the present invention, the polymer is preferably prepared by the following method:

Heating the polymer represented by formula I, thereby obtaining the Si-PFCB polymer of the present invention. The Si-PFCB polymer of the present invention prepared by the above method has the characteristics of simple preparation method and excellent performance of the prepared polymer.

The heating conditions are not particularly limited, preferably, the heating is performed at a temperature ranging from 150°C to 250°C.

Applications of low dielectric constant polymers containing hexafluorocyclobutyl ether and organosiloxane

The polymer of formula I described in the first aspect of the present invention and the polymer described in the fourth aspect of the present invention can be used to prepare a series of articles. In another preferred embodiment, the article is selected from the group consisting of: low dielectric Constant material, insulating material covered with metal wire, polymer sheet, polymer film.

Among them, a class of preferred products are products containing the Si-PFCB polymer of the present invention, and said products are preferably prepared by the following method: molding with a polymer of formula I to obtain a preform, and then The above preform is heated and solidified to obtain a product containing the Si-PFCB polymer of the present invention.

In a preferred example of the present invention, the described product containing the Si-PFCB polymer of the present invention is a polymer sheet or a polymer film, and the described product is prepared by the following method

Use the polymer of formula I to perform room temperature molding to obtain a polymer sheet; or dissolve the polymer of formula I with an organic solvent and form a film to obtain a polymer film, and then heat and cure the polymer sheet or polymer film , to obtain a polymer sheet or polymer film containing the Si-PFCB polymer of the present invention.

In another preferred example, the film forming process is spin coating film forming or drop coating film forming.

In another preferred example, the organic solvent is toluene, xylene, trimethylbenzene, diphenyl ether, cyclohexanone, chloroform, acetone, N,N-dimethylformamide, N,N-di Methylacetamide, dimethylsulfoxide, N-methylpyrrolidone, or combinations thereof.

The main advantages of the present invention include:

(1) Si-PFCB polymer provided by the present invention has good electrical properties and heat resistance, and the Si-PFCB polymer of the present invention prepared in a preferred example of the present invention has a dielectric constant as low as 2.33 (30MHz), 5% thermal decomposition temperature of 471°C, hardness of 0.392GPa, Young's modulus of 10.06GPa, and bonding strength with silicon wafer of 4.93GPa.

(2) The synthesis cost of the low dielectric material provided by the present invention is relatively low, and the preparation process is simple, and can be used as a class of high-performance electronic packaging materials or metal wire outsourcing materials with excellent thermal stability, low water absorption and low dielectric constant Coating, used in the fields of microelectronics processing industry and large motor manufacturing industry.

(3) The prepolymer provided by the present invention can be used to prepare polymers with good electrical properties, heat resistance and mechanical properties, and the preparation method is simple and suitable for industrial production.

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 without specific conditions indicated in the following examples, the conventional conditions or the conditions suggested by the manufacturer are usually followed. Percentages and parts are by weight unless otherwise indicated.

Preparation of Example 1 intermediate 14-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-bromobenzene

Under argon protection, 51.9 grams of 4-bromo-phenol (0.3mol), 147 grams of 1,2-dibromotetrafluoroethane (0.57mol) and 300 milliliters of DMSO (dimethylmethylene sulfone), stirred under ice-water bath for 30 minutes, then added 80 grams of anhydrous potassium carbonate (0.6mol), removed the ice-water bath, reacted at room temperature for 6 hours, poured the reaction mixture solution into water, stirred vigorously for 20 minutes, and washed with chloroform in batches The product was extracted, the extract was washed with saturated sodium chloride aqueous solution, and then the chloroform was removed by rotary evaporation. The concentrated solution was rectified to collect the 65°C/0.23mmHg component to obtain 98 g of the product, with a yield of 93%. Atmospheric boiling point 226～246℃, hydrogen spectrum characterization ( ¹ H NMR, 300MHz, CDCl ₃ , δin ppm): 7.51～7.53(d,2H), 7.11～7.13(d,2H); fluorine spectrum characterization ( ¹⁹ F NMR , 282MHz, CDCl ₃ , δin ppm): -86.2, (dt, 2F) - 68.2 (dt, 2F).

Example 2 Preparation of intermediate 14-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-bromobenzene

Under argon protection, 51.9 grams of 4-bromo-phenol (0.3mol), 147 grams of 1,2-dibromotetrafluoroethane (0.57mol) and 300 milliliters of N-methylpyrrolidone that are now steamed were added to the reaction apparatus, Stir in an ice-water bath for 30 minutes, then add 33.6 grams of potassium hydroxide (0.6 mol), remove the ice-water bath, react at room temperature for 6 hours, pour the reaction mixture into water, stir vigorously for 20 minutes, and extract the product in batches with chloroform. The extract was washed with a saturated sodium chloride aqueous solution, and then chloroform was removed by rotary evaporation. The concentrated solution was rectified to collect the 65°C/0.23mmHg component to obtain 84 g of the product, with a yield of 80%. Atmospheric boiling point 246～256℃, hydrogen spectrum characterization ( ¹ H NMR, 300MHz, CDCl ₃ , δin ppm): 7.51～7.53(d,2H), 7.11～7.13(d,2H); fluorine spectrum characterization ( ¹⁹ F NMR , 282MHz, CDCl ₃ , δin ppm): -86.2, (dt, 2F) - 68.2 (dt, 2F).

Embodiment 3 Intermediate 2: Preparation of 4-(1,2,2-trifluoroethyleneoxy)-1-bromobenzene

Under argon protection, 76 grams of 4-(2-bromo-1,1,2,2-tetrafluoroethoxy)-1-bromobenzene (0.22mol) obtained in Example 2 was added to the reaction flask, 480 ml Freshly distill acetonitrile, stir and dilute, add 30 g of zinc powder (0.5 mol), and heat up to reflux for 24 hours. Pour the reaction solution into 600 ml of water, stir for more than 15 minutes, extract with chloroform in batches, combine the chloroform extracts, wash with saturated aqueous sodium chloride, and dry over anhydrous sodium sulfate for more than 12 hours. Chloroform was removed by rotary evaporation, and the concentrated solution was rectified to collect the 56.2°C/0.6mmHg component to obtain 43.8 g of the product, with a yield of 61%. The boiling point of the product at normal pressure is 242-252°C, hydrogen spectrum characterization ( ¹ HNMR, 300MHz, CDCl ₃ , δin ppm): 7.47～7.49(d,2H), 6.99～7.01(d,2H); fluorine spectrum characterization ( ¹⁹ F NMR, 282MHz, CDCl ₃ , δin ppm): -134.2～-134.7(dd, 1F), -126.4～-125.8(dd, 1F), -119.4～-119.0(dd, 1F).

Example 4 Preparation of monomer 4-(1,2,2-trifluoroethyleneoxy)-1-(methyldiethoxysilyl)-benzene

Under the protection of argon, add 64.2 grams of methyltriethoxysilane (0.36mol) and 200 milliliters of freshly steamed tetrahydrofuran in the reaction flask, stir and dilute, add 15 grams of magnesium chips, stir vigorously at room temperature, add 31 grams of The intermediate 24-(1,2,2-trifluoroethyleneoxy)-1-bromobenzene obtained in Example 3 was stirred and reacted at room temperature for 24 hours after the addition was completed. The tetrahydrofuran and excess methyltriethoxysilane were removed by rotary evaporation, and the concentrated solution was rectified to collect the 62.7°C/0.6mmHg component to obtain 23 g of the product, with a yield of 59%. The normal pressure boiling point of the product is 258～262℃, and the hydrogen spectrum characterization ( ¹ H NMR, 300MHz, CDCl ₃ , δin ppm): 7.64～7.66(d,2H), 7.10～7.12(d,2H), 3.79～3.82(q ,4H), 1.22～1.25(t,6H), 0.35(s,3H); fluorine spectrum characterization ( ¹⁹ F NMR, 282MHz, CDCl ₃ ,δin ppm): -133.8～-134.2(dd,1F), -126.2 ～-126.7(dd, 1F), -119.4～-119.9(dd, 1F); carbon spectrum characterization ( ¹³ C NMR, 75MHz, CDCl ₃ , δin ppm): 156.7, 136.1, 131.5, 129.7, 115.2, 111.4, 58.3 ,18.0,-4.4.

Preparation of Example 5 Prepolymer Polymethyl-(1,2,2-trifluoroethyleneoxyphenyl)siloxane

Under argon protection, add 72mL toluene, 36mL water, 12mL acetic acid (0.21mol), 13.8 grams of monomer 4-(methyldiethoxysilyl)-(1,2 , 2-trifluoroethyleneoxy)benzene (45mmol), stirred at room temperature for 4 hours, and then aged at 85°C for 5 hours. Liquid separation, washing with water until neutral, rotary evaporation to remove the solvent, quantitatively obtain the product. Proton spectrum characterization ( ¹ H NMR, 300MHz, CDCl ₃ , δin ppm): 7.62～7.69(m,2H), 7.08～7.19(m,2H), 3.78～3.88(m,4H), 1.21～1.29(m, 6H), 0.22～0.61(m,3H); fluorine spectrum characterization ( ¹⁹ F NMR, 282MHz, CDCl ₃ ,δinppm): -134.1～-133.5(m,1F), -125.6～-126.4(m,1F), -119.1～-119.6(m,1F).

Preparation of Example 6 Prepolymer Polymethyl-(1,2,2-trifluoroethyleneoxyphenyl)siloxane

Under argon protection, add 36mL toluene, 18mL water, 3mL concentrated hydrochloric acid (0.25mol), 6.9 grams of 4-(methyldiethoxysilyl)-(1,2, 2-Trifluoroethyleneoxy)benzene (22.5 mmol), first stirred at room temperature for 4 hours, and then aged at 85°C for 5 hours. Liquid separation, washing with water until neutral, rotary evaporation to remove the solvent, quantitatively obtain the product. Proton spectrum characterization ( ¹ H NMR, 300MHz, CDCl ₃ , δin ppm): 7.62～7.69(m,2H), 7.08～7.19(m,2H), 3.78～3.88(m,4H), 1.21～1.29(m, 6H), 0.22～0.61(m,3H); fluorine spectrum characterization ( ¹⁹ F NMR, 282MHz, CDCl ₃ ,δinppm): -134.1～-133.5(m,1F), -125.6～-126.4(m,1F), -119.1～-119.6(m,1F).

Example 7 Spin coating and curing of prepolymer polymethyl-(1,2,2-trifluoroethyleneoxyphenyl) siloxane

Take 0.5 g of the prepolymer obtained in Example 6, dissolve it in 15 ml of toluene, filter the obtained solution with a 2-micron filter membrane, and drop it onto the strictly cleaned heavily doped On a silicon wafer (resistivity 2×10 ^-3 Ω.cm). After obtaining a thin film with a flat surface by spin coating in this way, it was placed in a nitrogen-protected tube furnace, and the solvent was removed at 150°C for 3 hours, and then the temperature was raised to 180°C for 18 hours or 250°C for 4 hours. A cured film was thus obtained.

Heat resistance, dielectric properties and mechanical properties of embodiment 8 polymer

Put the polymer film with a thickness of 170 nanometers prepared in Example 7 into a vacuum drying oven, heat at 200°C for 2 hours, cool to room temperature in a nitrogen atmosphere, and evaporate an aluminum electrode with a diameter of 1mm on the surface of the film , and evaporate metal aluminum with a thickness of 200 nanometers on the back of the silicon wafer, so as to obtain a standard film capacitor. By testing the capacitance of the film capacitor, the dielectric constant and dielectric loss factor of the film are calculated.

The above thin film obtained by spin coating was crushed, placed in a thermogravimetric analyzer, and the thermal decomposition temperature and carbon residue of the polymer were tested at a heating rate of 10°C/min.

The film obtained by spin-coating is subjected to nano-mechanical testing with a nano-integrated mechanical system to obtain nano-hardness, Young's modulus and bonding strength.

The specific data are shown in the table below:

Example 9 Use of Polymer as Printed Circuit Board Insulating Resin

Get 50 grams of the obtained prepolymer of Example 6, dissolve it in 200 milliliters of toluene, and at room temperature, apply the solution to the alkali-free glass cloth (600 g/m ² ), after removing the solvent at 120°C for 3 hours, the obtained glass fiber prepreg laminate (4 layers) was then placed in a flat vulcanizer, and pressed at a pressure of 20Kg/ ^cm2 and a temperature of 180°C. The formed glass fiber board is kept at 250° C. for 4 hours to obtain a cured glass fiber composite material, which can be directly used to manufacture printed circuit boards.

The obtained glass fiber board has a water absorption rate of 0.12%, a dielectric constant of 2.8 at the operating frequency (50Hz) of electrical equipment, and a dielectric loss tangent of 4×10 ^-3 , which are lower than those currently used in the industry. And polyimide and other glass fiber reinforced composite materials prepared as matrix resin.

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 (11)

1. a kind of polymer shown in formula I：

In formula, n >=2.

2. polymer as claimed in claim 1, it is characterised in that n=5～100.

3. polymer as claimed in claim 1, it is characterised in that n=10～20.

4. the preparation method of Formulas I polymer as claimed in claim 1, it is characterised in that including step：

In atent solvent, polymerization is hydrolyzed instead with the organic silicon monomer containing trifluoro vinyl ether unit as shown in Formula Il Should, obtain Formulas I polymer；

Wherein, R is selected from the group：C1-C4 alkyl；The definition of n is as described in the appended claim 1.

5. preparation method as claimed in claim 4, it is characterised in that described hydrolytic-polymeric reaction acidic catalyst and/or Carry out in the presence of water.

6. the purposes of Formulas I polymer as claimed in claim 1, it is characterised in that for being heating and curing, it is solid so as to prepare Fluidized polymer.

7. a kind of polymer, it is characterised in that described polymer be carried out with Formulas I polymer as claimed in claim 1 it is solid Change what is prepared.

8. the preparation method of polymer as claimed in claim 7, it is characterised in that the polymer is made by the following method It is standby：Formulas I polymer of the heating as shown in claim 1, so as to obtain polymer as claimed in claim 6.

9. method as claimed in claim 8, it is characterised in that the temperature range of the heating is 150～250 DEG C.

10. a kind of product, it is characterised in that the product contains Formulas I polymer as claimed in claim 1 or such as claim Polymer described in 7, or the product is with Formulas I polymer as claimed in claim 1 or as claimed in claim 7 is polymerized Prepared by thing.

11. products as claimed in claim 10, it is characterised in that described product is containing the polymerization described in claim 7 The sheet material or thin film of thing, and described product is prepared by the following method：

Room temperature molding is carried out with the Formulas I polymer described in claim 1 and obtains the sheet material containing Formulas I polymer；Or with organic molten Agent is dissolved the Formulas I polymer and carries out film forming, obtains the thin film containing Formulas I polymer；

Above-mentioned polymer sheet or polymeric film are heating and curing, are obtained containing polymer as claimed in claim 7 Sheet material or thin film.