Fluorine-containing monomer, fluorine-containing epoxy resin and preparation method thereof

Abstract

The present invention relates to a fluorine-containing monomer, a fluorine-containing epoxy resin and a preparation method thereof, and belongs to the technical field of polymer materials. The structural formula of the fluorine-containing monomer is shown in the following formula (I): wherein R1, R2, R3 and R4 are H, F, CH3, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH2=CH-, CH≡C-, CH3O- or C6H5CH2-. The fluorine-containing epoxy resin prepared by the present invention has a small molecular weight and low viscosity, which is conducive to molding and processing, high heat resistance, a fluorine content greater than 25wt.%, and the designed synthesis reaction conditions are mild, the process route is short, and it is conducive to engineering applications. The fluorine-containing epoxy resin of the present invention has the advantages of high heat resistance, low dielectric constant and low water absorption, and can be applied in the fields of functional coatings, composite materials, communication technology and electronic packaging. The method of the present invention has lower costs, safer production and high yield. #imgabs0#

Description

Technical Field

[0001] The present invention relates to a fluorine-containing monomer, a fluorine-containing epoxy resin and a preparation method thereof, and belongs to the technical field of polymer materials. Background Art

[0002] Epoxy resins offer excellent mechanical properties, heat resistance, and insulation properties. They possess high resistivity, low electrical conductivity loss, excellent adhesion to various materials, and excellent chemical stability. They are widely used in transistor and printed circuit board (PCB) coating and encapsulation applications. The epoxy resin curing process often produces a large number of secondary hydroxyl groups that readily absorb water. The resulting increased number of oriented dipoles or interfaces increases polarization dielectric loss. Excessive dielectric loss can cause heating and heat accumulation in the PCB, dielectric, or package, accelerating component aging and leading to device failure. Dielectric loss in the substrate not only causes heat during signal transmission but also leads to electrical signal loss, resulting in signal delays and even distortion. However, epoxy resins' water absorption and dielectric constant are not ideal (Dk ≈ 3-4), failing to meet the substrate performance requirements for next-generation high-frequency, high-speed communications. Therefore, developing epoxy resins with both low dielectric constants and low dielectric loss has become an important research direction.

[0003] Fluorine in organic fluorine materials has a small atomic radius and strong electronegativity, allowing it to dissociate onto the surface of the material, shielding the CC and making it more stable. Furthermore, its short bond distance, low polarity, low surface energy, and poor adhesion contribute to its numerous advantages. Therefore, fluorine-containing compounds offer numerous advantages, including stable performance, heat and chemical resistance, self-lubrication, weatherability, non-flammability, and hydrophobicity and oleophobicity. Introducing fluorine into epoxy resins not only maintains the epoxy resin's excellent bonding properties but also improves its wear resistance, corrosion resistance, pollution resistance, moisture resistance, dielectric properties, flame retardancy, heat resistance, and durability. Consequently, fluorine-containing epoxy resins are attracting increasing attention.

[0004] The preparation methods of fluorine-containing epoxy resins can be summarized into two types: physical blending and chemical synthesis. The physical blending method has a simple process, is easy to operate, and has low requirements for reaction conditions, but is prone to problems such as uneven dispersion and uneven structure, which affects the stability of performance; the chemical synthesis method connects the fluorine element to the resin molecular chain in the form of a chemical bond, and the internal structure of the product is uniform and the performance is stable. Currently, there are many studies on this method. Alberto et al. (EP Pat.293889) disclosed a series of preparation methods for fluorine-containing epoxy resins containing hexafluoroisopropyl, pointing out that the invented fluorine-containing epoxy resins have hydrophobic and oleophobic surface properties and a low friction coefficient, and the dielectric constant of the cured product is 3.1 to 3.2. CN201210100139.4 discloses a preparation method for fluorine-containing epoxy resins. The invented epoxy resin has the advantages of high glass transition temperature, excellent electrical properties, water absorption and strong hydrophobicity. Wang et al. [Journal of Applied Polymer Science, 2011, 124: 2615-2624] synthesized a fluorinated epoxy resin (DGEBF) using bisphenol AF and epichlorohydrin, blended it with commercial epoxy resin, and cured it with 4,4'-diaminodiphenylmethane (DDM). The results showed that with the increase of DGEBF content in the blending system, the glass transition temperature and thermal decomposition temperature (T 5％ ) gradually decreased, but its dielectric properties gradually improved (Dk = 2.03 ~ 3.80, Df = 0.018 ~ 0.030 @ 1MHz). Yin et al. [Journal of Applied Polymer Science, 2013, 130 (4): 2801-2808] synthesized 2,2-bisphenol hexafluoropropane diglycidyl ether (DGEBF) and thermally cured DGEBF with methylhexahydrophthalic anhydride (MHHPA) to obtain DGEBF / MHHPA low dielectric material. Tests and studies have shown that the glass transition temperature of this material is 147 ° C. Compared with the cured DGEBA resin, the introduction of bis-trifluoromethyl groups can enhance its dielectric properties. The Dk value of DGEBF / MHHPA is 2.93 @ 50Hz and the Df is 0.0065 @ 50Hz. At the same time, compared with non-fluorinated resins, the water absorption rate of fluorinated epoxy resin is also lower (0.2989%). In addition to using bisphenol AF as a raw material, Ge et al. [Polymer Journal, 2007, 39(11): 1135-1142] used Lewis acid to catalyze the reaction of 4-methoxy-2,2,2-trifluoroacetophenone and phenol to generate an intermediate, and then demethylated it to generate a fluorinated triphenol. Fluorinated epoxy resin (TEF) was further prepared by epoxidation with epichlorohydrin and cured with MHHPA and 4,4'-diaminodiphenyl sulfone, respectively. The experimental results show that the fluorinated epoxy resin has good thermal stability (T g=210~287℃), high decomposition temperature (T 5％ =363~388℃), excellent mechanical properties (flexural strength of 64~115MPa, flexural modulus of 2.29~2.65GPa) and low thermal expansion coefficient (46.7~59.6ppm / ℃). At the same time, TEF epoxy resin exhibits excellent low hygroscopicity (0.31~0.87%) and dielectric properties (Dk=3.2~3.5, tan d=1.52~3.14×10 -3 @1MHz). Summary of the Invention

[0005] The first object of the present invention is to provide a new fluorine-containing monomer.

[0006] To achieve the first object of the present invention, the structural formula of the fluorine-containing monomer is shown in the following formula (I):

[0007]

[0008] Wherein R1, R2, R3 and R4 are H, F, CH3, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH2=CH-, CH≡C-, CH3O- or C6H5CH2-.

[0009] In one embodiment, at least one of R3 and R4 is F.

[0010] In one embodiment, the method for preparing the fluorinated monomer comprises:

[0011] Step I: mixing an aniline derivative represented by formula (II), hexafluoroacetone trihydrate, and a catalyst, heating to 80-120° C. under inert gas protection for reaction for 3-12 hours, and purifying to obtain a 2-(4-aminophenyl)hexafluoroisopropanol derivative represented by formula (III);

[0012]

[0013] Step II: epichlorohydrin, an auxiliary agent and solvent II are mixed, stirred at 80-300 rpm under inert gas protection and heated to a temperature of 30-50° C., and then the 2-(4-aminophenyl)hexafluoroisopropanol derivative is added in 3-5 batches, with an interval of 55-65 minutes between each batch. After the addition is completed, the temperature is raised to 50-60° C. and the reaction is carried out for 3-8 hours. Alkali solution is then added dropwise in 2-5 batches, with an interval of 40-50 minutes between each batch. After the addition is completed, the temperature is raised to 55-60° C. and the reaction is carried out for 4.5-12 hours to purify the fluorinated monomer;

[0014] Wherein, the catalyst described in step 1 is p-toluenesulfonic acid, H2SO4, HCl, H6P4O13 , AlCl3, niobium pentoxide and BF3·Et2O;

[0015] The auxiliary agent in step II is at least one of tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, and hexadecyltrimethylammonium bromide.

[0016] In one specific embodiment, the molar ratio of the aniline derivative, hexafluoroacetone trihydrate and catalyst in step I is 1:1.5-2.3:0.18-0.23.

[0017] The inert gases described in the present invention are gases that do not react with the reaction system, such as nitrogen.

[0018] In one embodiment, the purification in step I comprises: cooling to room temperature after the reaction is completed, adding solvent I to dilute and dissolve, filtering, washing, separating, and distilling the resulting solution under reduced pressure to remove excess hexafluoroacetone trihydrate; and then recrystallizing to obtain a purified 2-(4-aminophenyl)hexafluoroisopropanol derivative; the solvent I is preferably at least one of chloroform, dichloromethane, benzene, toluene, xylene, ethanol, and isopropanol;

[0019] The purification in step II preferably includes: cooling to room temperature after the reaction is completed, adding an organic solvent III for extraction, filtering, washing with water until neutral, separating the organic layer, drying the organic layer, filtering, and spinning the filtrate to obtain the multifunctional fluorine-containing epoxy resin; the organic solvent III is at least one of chloroform, dichloromethane, toluene, and xylene.

[0020] In a specific embodiment, the solvent II is at least one of benzene, toluene, xylene, methanol, ethanol, isopropanol, and acetone.

[0021] In one embodiment, the molar ratio of the 2-(4-aminophenyl)hexafluoroisopropanol derivative, epichlorohydrin, auxiliary agent, solvent II and base in step II is 1:18-22:0-0.5:6.5-10:3.2-3.8.

[0022] In a specific embodiment, the alkali solution in step II is at least one of a sodium hydroxide solution and a potassium hydroxide solution; the mass fraction of the alkali solution is preferably 30% to 45%;

[0023] Preferably, the total time for adding the 2-(4-aminophenyl)hexafluoroisopropanol derivative is 2.5 to 5.5 hours, including the addition time and interval time of each batch, that is, the total time from the start of dropwise addition of the 2-(4-aminophenyl)hexafluoroisopropanol derivative to the complete addition of the 2-(4-aminophenyl)hexafluoroisopropanol derivative;

[0024] The total time for adding the alkali solution is 70 to 250 minutes, including the addition time and interval time of each batch, that is, the total time from the beginning of adding the alkali solution to the complete addition of the alkali solution.

[0025] A second object of the present invention is to provide a fluorine-containing epoxy resin.

[0026] To achieve the second object of the present invention, the fluorine-containing epoxy resin is obtained by curing the above-mentioned fluorine-containing monomer; the curing is curing with a curing agent or UV curing, and the curing agent is preferably at least one of 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene or hexahydrophthalic anhydride;

[0027] The molecular weight of the fluorinated epoxy resin is in the range of 400 to 2000, and the viscosity is in the range of 900 mPa·s to 1300 mPa·s; the dielectric constant of the fluorinated epoxy resin is 2.3C 2 / (N·M 2 )~2.8C 2 / (N·M 2 ), and the saturated water absorption rate is preferably 0.8% to 3.2%.

[0028] The third object of the present invention is to provide a method for preparing the above-mentioned fluorine-containing monomer.

[0029] To achieve the third object of the present invention, the method for preparing the fluorine-containing monomer comprises:

[0030] Step I: mixing an aniline derivative represented by formula (II), hexafluoroacetone trihydrate, and a catalyst, heating to 80-120° C. under inert gas protection for reaction for 3-12 hours, and purifying to obtain a 2-(4-aminophenyl)hexafluoroisopropanol derivative represented by formula (III);

[0031]

[0032] Step II: epichlorohydrin, an auxiliary agent and solvent II are mixed, stirred at 80-300 rpm under inert gas protection and heated to a temperature of 30-50° C., and then the 2-(4-aminophenyl)hexafluoroisopropanol derivative is added in 3-5 batches, with an interval of 55-65 minutes between each batch. After the addition is completed, the temperature is raised to 50-60° C. and the reaction is carried out for 3-8 hours. Alkali solution is then added dropwise in 2-5 batches, with an interval of 40-50 minutes between each batch. After the addition is completed, the temperature is raised to 55-60° C. and the reaction is carried out for 4.5-12 hours to purify the fluorinated monomer;

[0033] Wherein, the catalyst described in step 1 is p-toluenesulfonic acid, H2SO4, HCl, H6P4O 13, AlCl3, niobium pentoxide and BF3·Et2O;

[0034] The auxiliary agent in step II is at least one of tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, and hexadecyltrimethylammonium bromide;

[0035] The molar ratio of the aniline derivative, hexafluoroacetone trihydrate and catalyst in step I is preferably 1:1.5-2.3:0.18-0.23;

[0036] The solvent II is preferably at least one of benzene, toluene, xylene, methanol, ethanol, isopropanol, and acetone;

[0037] The molar ratio of the 2-(4-aminophenyl)hexafluoroisopropanol derivative, epichlorohydrin, auxiliary agent, solvent II and base in step II is preferably 1:18-22:0-0.5:6.5-10:3.2-3.8.

[0038] Beneficial effects:

[0039] 1. The fluorinated epoxy resin prepared by the present invention has a small molecular weight and low viscosity, which is conducive to molding and processing. It has high heat resistance and a fluorine content greater than 25wt.%. In addition, the designed synthesis reaction conditions are mild and the process route is short, which is conducive to engineering applications.

[0040] 2. The fluorine-containing epoxy resin of the present invention has the advantages of high heat resistance, low dielectric constant and low water absorption, and can be used in functional coatings, composite materials, communication technology and electronic packaging fields.

[0041] 3. Based on molecular structure design, the present invention uses inexpensive aniline and its derivatives as raw materials, and reacts them with the safer hexafluoroacetone trihydrate via a Friedel-Crafts reaction to synthesize 2-(4-aminophenyl)hexafluoroisopropanol derivatives. This reduces costs and makes production safer.

[0042] 4. The reaction raw materials contain fluorine element, which has low reaction activity and is not easy to proceed. The method of the present invention has a high yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 These are infrared spectra of 2-(4-aminophenyl)hexafluoroisopropanol (HFA) prepared in Example 4 and 2-(4-amino-3,5-dimethylphenyl)-hexafluoroisopropanol (HFDMA) prepared in Example 2.

[0044] Figure 2These are the hydrogen NMR spectra of 2-(4-aminophenyl)hexafluoroisopropanol (HFA) prepared in Example 4 and 2-(4-amino-3,5-dimethylphenyl)-hexafluoroisopropanol (HFDMA) prepared in Example 2.

[0045] Figure 3 These are infrared spectra of 2-(4-aminophenyl)hexafluoroisopropanol epoxide (HFAEP) prepared in Example 4 and 2-(4-amino-3,5-dimethylphenyl)hexafluoroisopropanol epoxide (HFDMAEP) prepared in Example 2.

[0046] Figure 4 These are the hydrogen NMR spectra of 2-(4-aminophenyl)hexafluoroisopropanol epoxide (HFAEP) prepared in Example 4 and 2-(4-amino-3,5-dimethylphenyl)-hexafluoroisopropanol epoxide (HFDMAEP) prepared in Example 2. DETAILED DESCRIPTION

[0047] To achieve the first object of the present invention, the structural formula of the fluorine-containing monomer is shown in the following formula (I):

[0048]

[0049] Wherein R1, R2, R3 and R4 are H, F, CH3, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH2=CH-, CH≡C-, CH3O- or C6H5CH2-.

[0050] In one embodiment, at least one of R3 and R4 is F.

[0051] In one embodiment, the method for preparing the fluorinated monomer comprises:

[0052] Step I: mixing an aniline derivative represented by formula (II), hexafluoroacetone trihydrate, and a catalyst, heating to 80-120° C. under inert gas protection for reaction for 3-12 hours, and purifying to obtain a 2-(4-aminophenyl)hexafluoroisopropanol derivative represented by formula (III);

[0053]

[0054] The synthetic reaction is as follows:

[0055]

[0056] Step II: epichlorohydrin, an auxiliary agent and solvent II are mixed, stirred at 80-300 rpm under inert gas protection and heated to a temperature of 30-50° C., and then the 2-(4-aminophenyl)hexafluoroisopropanol derivative is added in 3-5 batches, with an interval of 55-65 minutes between each batch. After the addition is completed, the temperature is raised to 50-60° C. and the reaction is carried out for 3-8 hours. Alkali solution is then added dropwise in 2-5 batches, with an interval of 40-50 minutes between each batch. After the addition is completed, the temperature is raised to 55-60° C. and the reaction is carried out for 4.5-12 hours to purify the fluorinated monomer;

[0057] The synthetic reaction is as follows:

[0058]

[0059] Wherein, the catalyst described in step 1 is p-toluenesulfonic acid, H2SO4, HCl, H6P4O 13 , AlCl3, niobium pentoxide and BF3·Et2O;

[0060] The auxiliary agent in step II is at least one of tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, and hexadecyltrimethylammonium bromide.

[0061] In one specific embodiment, the molar ratio of the aniline derivative, hexafluoroacetone trihydrate and catalyst in step I is 1:1.5-2.3:0.18-0.23.

[0062] The inert gases described in the present invention are gases that do not react with the reaction system, such as nitrogen.

[0063] In one embodiment, the purification in step I comprises: cooling to room temperature after the reaction is completed, adding solvent I to dilute and dissolve, filtering, washing, separating, and distilling the resulting solution under reduced pressure to remove excess hexafluoroacetone trihydrate; and then recrystallizing to obtain a purified 2-(4-aminophenyl)hexafluoroisopropanol derivative; the solvent I is preferably at least one of chloroform, dichloromethane, benzene, toluene, xylene, ethanol, and isopropanol;

[0064] The purification in step II preferably includes: cooling to room temperature after the reaction is completed, adding an organic solvent III for extraction, filtering, washing with water until neutral, separating the organic layer, drying the organic layer, filtering, and spinning the filtrate to obtain the multifunctional fluorine-containing epoxy resin; the organic solvent III is at least one of chloroform, dichloromethane, toluene, and xylene.

[0065] In a specific embodiment, the solvent II is at least one of benzene, toluene, xylene, methanol, ethanol, isopropanol, and acetone.

[0066] In one embodiment, the molar ratio of the 2-(4-aminophenyl)hexafluoroisopropanol derivative, epichlorohydrin, auxiliary agent, solvent II and base in step II is 1:18-22:0-0.5:6.5-10:3.2-3.8.

[0067] In a specific embodiment, the alkali solution in step II is at least one of a sodium hydroxide solution and a potassium hydroxide solution; the mass fraction of the alkali solution is preferably 30% to 45%;

[0068] Preferably, the total time for adding the 2-(4-aminophenyl)hexafluoroisopropanol derivative is 2.5 to 5.5 hours, including the addition time and interval time of each batch, that is, the total time from the start of dropwise addition of the 2-(4-aminophenyl)hexafluoroisopropanol derivative to the complete addition of the 2-(4-aminophenyl)hexafluoroisopropanol derivative;

[0069] The total time for adding the alkali solution is 70 to 250 minutes, including the addition time and interval time of each batch, that is, the total time from the beginning of adding the alkali solution to the complete addition of the alkali solution.

[0070] A second object of the present invention is to provide a fluorine-containing epoxy resin.

[0071] To achieve the second object of the present invention, the fluorine-containing epoxy resin is obtained by curing the above-mentioned fluorine-containing monomer; the curing is curing with a curing agent or UV curing, and the curing agent is preferably at least one of 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, and hexahydrophthalic anhydride;

[0072] The molecular weight of the fluorinated epoxy resin is in the range of 400 to 2000, and the viscosity is in the range of 900 mPa·s to 1300 mPa·s; the dielectric constant of the fluorinated epoxy resin is 2.3C 2 / (N·M 2 )~2.8C 2 / (N·M 2 ), and the saturated water absorption rate is preferably 0.8% to 3.2%.

[0073] The third object of the present invention is to provide a method for preparing the above-mentioned fluorine-containing monomer.

[0074] To achieve the third object of the present invention, the method for preparing the fluorine-containing monomer comprises:

[0075] Step I: mixing an aniline derivative represented by formula (II), hexafluoroacetone trihydrate, and a catalyst, heating to 80-120° C. under inert gas protection for reaction for 3-12 hours, and purifying to obtain a 2-(4-aminophenyl)hexafluoroisopropanol derivative represented by formula (III);

[0076]

[0077] Step II: epichlorohydrin, an auxiliary agent and solvent II are mixed, stirred at 80-300 rpm under inert gas protection and heated to a temperature of 30-50° C., and then the 2-(4-aminophenyl)hexafluoroisopropanol derivative is added in 3-5 batches, with an interval of 55-65 minutes between each batch. After the addition is completed, the temperature is raised to 50-60° C. and the reaction is carried out for 3-8 hours. Alkali solution is then added dropwise in 2-5 batches, with an interval of 40-50 minutes between each batch. After the addition is completed, the temperature is raised to 55-60° C. and the reaction is carried out for 4.5-12 hours to purify the fluorinated monomer;

[0078] Wherein, the catalyst described in step 1 is p-toluenesulfonic acid, H2SO4, HCl, H6P4O 13 , AlCl3, niobium pentoxide and BF3·Et2O;

[0079] The auxiliary agent in step II is at least one of tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, and hexadecyltrimethylammonium bromide;

[0080] The molar ratio of the aniline derivative, hexafluoroacetone trihydrate and catalyst in step I is preferably 1:1.5-2.3:0.18-0.23;

[0081] The solvent II is preferably at least one of benzene, toluene, xylene, methanol, ethanol, isopropanol, and acetone;

[0082] The molar ratio of the 2-(4-aminophenyl)hexafluoroisopropanol derivative, epichlorohydrin, auxiliary agent, solvent II and base in step II is preferably 1:18-22:0-0.5:6.5-10:3.2-3.8.

[0083] The specific embodiments of the present invention are further described below in conjunction with examples, but the present invention is not limited to the scope of the examples.

[0084] Example 1

[0085] The preparation method of the novel high-performance fluorine-containing epoxy resin of this embodiment comprises the following steps:

[0086] (1) In a single-necked flask equipped with a condenser, 36.35 g (0.3 mol) of 3,5-dimethylaniline, 127.17 g (0.6 mol) of hexafluoroacetone trihydrate (HFA) were added. 3H2O) and 8.00g (0.06mol) aluminum chloride were heated to 105°C under nitrogen protection for condensation reaction, and the temperature was kept for 7 hours; after the reaction solution was cooled to room temperature, the mixture obtained by the condensation reaction was added with ethanol to dilute and dissolve, filtered, washed, separated, and the obtained solution was distilled under reduced pressure to remove excess HFA 3H2O; the crude product was recrystallized from ethanol to obtain purified 2-(4-amino-2,6-dimethylphenyl)-hexafluoroisopropanol with a yield of 70.21%.

[0087] (2) Add 92.52g (1.0mol) of epichlorohydrin, 5.69g (0.025mol) of benzyltriethylammonium chloride and 15.82g (0.49mol) of methanol into a three-necked flask equipped with a stirrer, a condenser and a thermometer, and heat to 40°C with stirring at 80rpm under nitrogen protection. Then, add 14.36g (0.05mol) of 2-(4-amino-2,6-dimethylphenyl)-hexafluoroisopropanol in three times within 4 hours, with an interval of 60min each time. After the addition of the materials, the temperature was raised to 50°C and the reaction was carried out for 4 hours. Then, 18 g of a 40% sodium hydroxide aqueous solution was added to the reactor in three times over 2 hours, each time with an interval of 40 minutes. After the addition was completed, the temperature was raised to 55°C and the reaction was carried out for 4.5 hours. After the reaction solution was cooled to room temperature, chloroform was added for extraction, filtered, and the solution was washed with warm water until neutral. The organic layer was separated, dried, filtered, and the filtrate was dried to obtain 2-(4-amino-2,6-dimethylphenyl)-hexafluoroisopropanol epoxy with a yield of 94.67%.

[0088] 2-(4-Amino-2,6-dimethylphenyl)-hexafluoroisopropanol epoxy was cured with 4,4′-diaminodiphenyl sulfone (DDS) curing agent to obtain epoxy resin, the properties of which are detailed in Table 1.

[0089] Table 1 Properties of epoxy resin

[0090]

[0091]

[0092] Example 2

[0093] The preparation method of the novel high-performance fluorine-containing epoxy resin of this embodiment comprises the following steps:

[0094] (1) In a single-necked flask equipped with a condenser, 36.35 g (0.3 mol) of 2,6-dimethylaniline, 151.85 g (0.69 mol) of hexafluoroacetone trihydrate (HFA) were added. 3H2O) and 11.88g (0.069mol) of p-toluenesulfonic acid were heated to 120°C under nitrogen protection for condensation reaction, and the temperature was kept for 8 hours; after the reaction solution was cooled to room temperature, the mixture obtained by the condensation reaction was added with dichloromethane to dilute and dissolve, filtered, washed, separated, and the obtained solution was distilled under reduced pressure to remove excess HFA 3H2O; the crude product was recrystallized from ethanol to obtain purified 2-(4-amino-3,5-dimethylphenyl)-hexafluoroisopropanol (HFDMA) with a yield of 76.31%. The infrared spectrum and H-NMR spectrum of the product prepared in this example are shown in Figure 1 and Figure 2 .from Figure 1 It can be seen that at 3401cm -1 and 3327cm -1 Both peaks are attributed to the stretching vibration peaks of the amino group connected to the benzene ring, at 3084 cm -1 The peak at 1148 cm is attributed to the stretching vibration peak of hydroxyl. -1 The peak at is attributed to the characteristic peak of CF. Figure 2 The H NMR spectrum shows that 8.13 ppm is the proton hydrogen of -OH, 7.09 ppm is the proton hydrogen of the benzene ring, 4.91 ppm is the proton hydrogen of -NH2, and 2.12 is the proton hydrogen of -CH3. In addition, 3.36 and 2.51 ppm are the proton hydrogen of water and solvent, respectively.

[0095] (2) Add 101.78 g (1.1 mol) of epichlorohydrin and 20.34 g (0.35 mol) of acetone to a three-necked flask equipped with a stirrer, a condenser and a thermometer, and heat to 42°C with stirring at 90 rpm under nitrogen protection. Then, add 14.36 g (0.05 mol) of HFDMA in 4 portions over 5.5 hours, each time with an interval of 55 minutes. After the addition is completed, heat to 52°C and react for 4.5 hours. Then, add 101.78 g (1.1 mol) of epichlorohydrin and 20.34 g (0.35 mol) of acetone to the flask. Stir and heat to 42°C under nitrogen protection. 19 g of 40% sodium hydroxide aqueous solution was added in 4 portions over 50 min intervals. After the addition was complete, the temperature was raised to 58° C. and the reaction was continued for 5.5 h. After the reaction solution was cooled, dichloromethane was added for extraction, filtered, and the solution was washed with warm water until neutral. The organic layer was separated, dried, filtered, and the filtrate was dried to obtain light yellow 2-(4-amino-3,5-dimethylphenyl)-hexafluoroisopropanol epoxide (HFDMAEP) with a yield of 95.31%. The infrared spectrum and H-NMR spectrum of the product prepared in this example are shown in FIG. Figure 3 and Figure 4 .from Figure 3 It can be seen that at 910cm -1 The peak at 1215 cm is attributed to the characteristic peak of the epoxy group. -1 The peak at is attributed to the characteristic peak of COC in the epoxy group. Figure 4 It can be seen that 3.13 and 2.59-2.86 ppm are the proton hydrogens of -CH2- and -CH- in the epoxy group.

[0096] The obtained product was cured with 4,4′-diaminodiphenyl sulfone (DDS) curing agent to obtain an epoxy resin, the properties of which are detailed in Table 1.

[0097] Example 3

[0098] The preparation method of the novel high-performance fluorine-containing epoxy resin of this embodiment comprises the following steps:

[0099] (1) In a single-necked flask equipped with a condenser, 38.73 g (0.3 mol) of 2,6-difluoroaniline, 118.84 g (0.54 mol) of hexafluoroacetone trihydrate (HFA) were added. 3H2O) and 9.37g (0.066mol) of boron trifluoride ether were heated to 110°C under nitrogen protection for condensation reaction, and the temperature was kept for 6 hours; after the reaction solution was cooled to room temperature, the mixture obtained by the condensation reaction was added with chloroform to dilute and dissolve, filtered, washed, separated, and the obtained solution was distilled under reduced pressure to remove excess HFA 3H2O; the crude product was recrystallized from ethanol to obtain purified 2-(4-amino-3,5-difluorophenyl)-hexafluoroisopropanol with a yield of 65.34%.

[0100] (2) In a three-necked flask equipped with a stirrer, a condenser and a thermometer, 97.90 g (0.95 mol) of epichlorohydrin, 6.95 g (0.025 mol) of tetrabutylammonium chloride and 15.82 g (0.49 mol) of ethanol were added. The mixture was stirred at 150 rpm under nitrogen protection and heated to 35°C. Then, 14.76 g (0.05 mol) of 2-(4-amino-3,5-difluorophenyl)-hexafluoroisopropanol was added five times within 5 hours, with an interval of 55 minutes between each addition. After the addition is completed, the temperature is raised to 55°C and the reaction is carried out for 5 hours. Then, 18 g of a 40% sodium hydroxide aqueous solution is added to the reactor in 3 times over 2 hours, each time with an interval of 40 minutes. After the addition is completed, the temperature is raised to 55°C and the reaction is carried out for 4.5 hours. After the reaction liquid is cooled, chloroform is added for extraction, filtered, and the solution is washed with warm water until neutral. The organic layer is separated, the organic layer is dried, filtered, and the filtrate is dried to obtain 2-(4-amino-3,5-difluorophenyl)-hexafluoroisopropanol epoxy with a yield of 84.31%.

[0101] The obtained product was cured with 4,4′-diaminodiphenyl sulfone (DDS) curing agent to obtain an epoxy resin, the properties of which are detailed in Table 1.

[0102] Example 4

[0103] The preparation method of the novel high-performance fluorine-containing epoxy resin of this embodiment comprises the following steps:

[0104] (1) In a single-necked flask equipped with a condenser, 27.9 g (0.3 mol) of aniline, 99.03 g (0.45 mol) of hexafluoroacetone trihydrate (HFA) were added. 3H2O) and 14.35g (0.054mol) of niobium pentoxide were heated to 80°C under nitrogen protection for condensation reaction, and the temperature was kept for 3 hours; after the reaction solution was cooled to room temperature, the mixture obtained by the condensation reaction was added toluene to dilute and dissolve, and filtered, and the obtained solution was distilled under reduced pressure to remove excess HFA 3H2O; The crude product was recrystallized from ethanol to obtain purified 4-aminobenzene hexafluoroisopropanol (HFA) with a yield of 73.54%. The infrared spectrum and nuclear magnetic hydrogen spectrum of the product prepared in this example are shown in Figure 1 and Figure 2 .from Figure 1 It can be seen that at 3401cm -1 and 3327cm -1 Both peaks are attributed to the stretching vibration peaks of the amino group connected to the benzene ring, at 3084 cm -1 The peak at 1187 cm is attributed to the stretching vibration peak of hydroxyl. -1 The peak at 831 cm is attributed to the characteristic peak of CF. -1 The peak at is attributed to the characteristic peak of 1,4-disubstituted benzene ring. Figure 2 It can be seen that 8.18 ppm is the proton hydrogen of -OH, 7.29-7.31 and 6.61-6.63 ppm are the proton hydrogen of benzene ring, 5.44 ppm is the proton hydrogen of -NH2, 3.36 and 2.51 ppm are the proton hydrogen of water and solvent respectively.

[0105] (2) 83.27 g (0.9 mol) of epichlorohydrin and 14.97 g (0.325 mol) of ethanol were added to a three-necked flask equipped with a stirrer, a condenser and a thermometer. The mixture was stirred at 200 rpm and heated to 38°C under nitrogen protection. Then, 12.96 g (0.05 mol) of HFA was added three times within 2.5 hours, each time with an interval of 55 minutes. After the addition was completed, the temperature was raised to 51°C and the reaction was carried out for 3.5 hours. Then, 16 g of a 40% sodium hydroxide aqueous solution was added to the reactor twice within 70 minutes, each time with an interval of 50 minutes. After the addition was completed, the temperature was raised to 56°C and the reaction was carried out for 4.5 hours. After the reaction solution was cooled, dichloromethane was added for extraction, and the solution was filtered with suction. The solution was washed with warm water until it was neutral, the organic layer was separated, the organic layer was dried, filtered, and the filtrate was spin-dried to obtain light yellow 4-aminobenzene hexafluoroisopropanol epoxide (HFAEP) with a yield of 93.51%. The infrared spectrum and nuclear magnetic hydrogen spectrum of the product prepared in this example are shown in Figure 3 and Figure 4 .Depend on Figure 3 It can be seen that at 910cm -1 The peak at 1215 cm is attributed to the characteristic peak of the epoxy group. -1 The peak at is attributed to the characteristic peak of COC in the epoxy group. Figure 4 It can be seen that 3.13 and 2.59-2.86 ppm are the proton hydrogens of -CH2- and -CH- in the epoxy group.

[0106] The obtained product was cured with 4,4′-diaminodiphenyl sulfone (DDS) curing agent to obtain an epoxy resin, the properties of which are detailed in Table 1.

[0107] Example 5

[0108] The preparation method of the novel high-performance fluorine-containing epoxy resin of this embodiment comprises the following steps:

[0109] (1) In a single-necked flask equipped with a condenser, 38.73 g (0.3 mol) of 3,5-difluoroaniline, 112.24 g (0.51 mol) of hexafluoroacetone trihydrate (HFA) were added. 3H2O) and 16.75g (0.063mol) of niobium pentoxide were heated to 90°C under nitrogen protection for condensation reaction, and the temperature was kept for 5 hours; after the reaction solution was cooled to room temperature, the mixture obtained by the condensation reaction was added with ethanol to dilute and dissolve, filtered, and the obtained solution was distilled under reduced pressure to remove excess HFA 3H2O; the crude product was recrystallized from ethanol to obtain purified 2-(4-amino-2,6-difluorophenyl)-hexafluoroisopropanol with a yield of 65.34%.

[0110] (2) Add 101.78 g (1.1 mol) of epichlorohydrin and 20.34 g (0.35 mol) of acetone to a three-necked flask equipped with a stirrer, a condenser and a thermometer, stir and heat at 253 rpm under nitrogen protection to 42°C, then add 14.76 g (0.05 mol) of 2-(4-amino-2,6-difluorophenyl)-hexafluoroisopropanol in 5 times over 5.5 hours, each time for 60 minutes. After the addition is completed, heat to 52°C and react. The reaction mixture was stirred for 4.5 hours, and then 19 g of a 40% sodium hydroxide aqueous solution was added to the reactor in 4 times over 250 minutes, with an interval of 50 minutes each time. After the addition was completed, the temperature was raised to 58°C and the reaction was continued for 5.5 hours. After the reaction solution was cooled, chloroform was added for extraction, filtered, and the solution was washed with warm water until neutral. The organic layer was separated, dried, filtered, and the filtrate was dried to obtain 2-(4-amino-2,6-difluorophenyl)-hexafluoroisopropanol epoxy with a yield of 86.54%.

[0111] The obtained product was cured with 4,4′-diaminodiphenyl sulfone (DDS) curing agent to obtain an epoxy resin, the properties of which are detailed in Table 1.

[0112] Example 6

[0113] The preparation method of the novel high-performance fluorine-containing epoxy resin of this embodiment comprises the following steps:

[0114] (1) In a single-necked flask equipped with a condenser, 44.77 g (0.3 mol) of 2,6-diethylaniline, 151.85 g (0.69 mol) of hexafluoroacetone trihydrate (HFA) were added. 3H2O) and 23.32g (0.069mol) of polyphosphoric acid were heated to 95°C under nitrogen protection for condensation reaction, and the temperature was kept for 4 hours; after the reaction solution was cooled to room temperature, the mixture obtained by the condensation reaction was added with ethanol to dilute and dissolve, filtered, and the obtained solution was distilled under reduced pressure to remove excess HFA 3H2O; the crude product was recrystallized from ethanol to obtain purified 2-(4-amino-3,5-diethylphenyl)-hexafluoroisopropanol with a yield of 76.34%.

[0115] (2) Add 97.15 g (1.05 mol) of epichlorohydrin and 21.04 g (0.35 mol) of isopropyl alcohol to a three-necked flask equipped with a stirrer, a condenser, and a thermometer. Stir and heat at 300 rpm under nitrogen protection until the temperature reaches 38°C. Then, add 15.76 g (0.05 mol) of 2-(4-amino-3,5-diethylphenyl)-hexafluoroisopropanol in 4 times over 4 hours, with an interval of 55 minutes each time. After the addition is completed, heat to 60°C. The reaction was carried out for 3.5 hours, and then 16 g of a 40% sodium hydroxide aqueous solution was added to the reactor three times over 150 minutes, each time with an interval of 45 minutes. After the addition was completed, the temperature was raised to 60°C and the reaction was continued for 4.5 hours. After the reaction solution was cooled, xylene was added for extraction, filtered, and the solution was washed with warm water until neutral. The organic layer was separated, dried, filtered, and the filtrate was dried to obtain 2-(4-amino-3,5-diethylphenyl)-hexafluoroisopropanol epoxy with a yield of 82.95%.

[0116] The obtained product was cured with 4,4′-diaminodiphenyl sulfone (DDS) curing agent to obtain an epoxy resin, the properties of which are detailed in Table 1.

[0117] Comparative Example 1

[0118] In the synthesis of step II, the 2-(aminophenyl)hexafluoroisopropanol derivative and the alkali solution are added directly without batching or adding them continuously. When the reaction is completed, the entire system turns black and the viscosity increases. Post-processing is difficult to carry out and no product is obtained.

Claims

1. A fluorinated monomer, characterized in that The structural formula of the fluorine-containing monomer is shown in the following formula (I): Formula (I) Wherein R1, R2, R3 and R4 are H, F, CH3, CH3CH2-, CH3CH2CH2-, CH3CH2CH2CH2-, CH2=CH-, CH≡C-, CH3O- or C6H5CH2-.

2. The fluorinated monomer according to claim 1, wherein At least one of R3 and R4 is F.

3. The method for preparing a fluorinated monomer according to claim 1 or 2, wherein: The preparation method of the fluorine-containing monomer comprises: Step I: Mixing an aniline derivative represented by formula (II), hexafluoroacetone trihydrate, and a catalyst, heating to 80-120°C under inert gas protection for 3-12 hours, and purifying to obtain a 2-(4-aminophenyl)hexafluoroisopropanol derivative represented by formula (III); Formula (II) Formula (III) Step II: epichlorohydrin, an auxiliary agent, and solvent II are mixed, stirred at 80 to 300 rpm under inert gas protection and heated to a temperature of 30 to 50 ° C, and then the 2-(4-aminophenyl) hexafluoroisopropanol derivative is added in 3 to 5 batches, with an interval of 55 to 65 minutes between each batch. After the addition is completed, the temperature is raised to 50 to 60 ° C and the reaction is carried out for 3 to 8 hours. Then, an alkali solution is added dropwise in 2 to 5 batches, with an interval of 40 to 50 minutes between each batch. After the addition is completed, the temperature is raised to 55 to 60 ° C and the reaction is carried out for 4.5 to 12 hours to purify the fluorinated monomer; Wherein, the catalyst described in step 1 is p-toluenesulfonic acid, H2SO4, HCl, H6P4O 13 , AlCl3, niobium pentoxide and BF3·Et2O; The auxiliary agent in step II is at least one of tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, and hexadecyltrimethylammonium bromide.

4. The method for preparing a fluorinated monomer according to claim 3, wherein: The molar ratio of the aniline derivative, hexafluoroacetone trihydrate and catalyst in step I is 1: 1.5-2.3: 0.18-0.

23.

5. The method for preparing a fluorinated monomer according to claim 3, wherein: The purification in step I comprises: cooling to room temperature after the reaction is completed, adding solvent I to dilute and dissolve, filtering, washing, separating the liquids, and distilling the obtained solution under reduced pressure to remove excess hexafluoroacetone trihydrate; and then recrystallizing to obtain a purified 2-(4-aminophenyl)hexafluoroisopropanol derivative.

6. The method for preparing a fluorinated monomer according to claim 5, wherein: The solvent I is at least one of chloroform, dichloromethane, benzene, toluene, xylene, ethanol, and isopropanol.

7. The method for preparing a fluorinated monomer according to claim 3, wherein: The purification in step II includes: cooling to room temperature after the reaction is completed, adding an organic solvent III for extraction, filtering, washing with water until neutral, separating the organic layer, drying the organic layer, filtering, and spinning the filtrate to obtain a fluorine-containing monomer; the organic solvent III is at least one of chloroform, dichloromethane, toluene, and xylene.

8. The method for preparing a fluorine-containing monomer according to claim 3, wherein: The solvent II is at least one of benzene, toluene, xylene, methanol, ethanol, isopropanol, and acetone.

9. The method for preparing a fluorine-containing monomer according to claim 3, wherein: The molar ratio of the 2-(4-aminophenyl)hexafluoroisopropanol derivative, epichlorohydrin, auxiliary agent, solvent II and base in step II is 1:18-22:0-0.5:6.5-10:3.2-3.

8.

10. The method for preparing a fluorine-containing monomer according to claim 3, wherein: The alkali solution in step II is at least one of a sodium hydroxide solution and a potassium hydroxide solution.

11. The method for preparing a fluorine-containing monomer according to claim 10, wherein: The mass fraction of the alkali solution is 30% to 45%.

12. The method for preparing a fluorine-containing monomer according to claim 3, wherein: The total time for adding the 2-(4-aminophenyl)hexafluoroisopropanol derivative is 2.5 to 5.5 hours, and the total time for adding the alkali solution dropwise is 70 to 250 minutes.

13. Fluorine-containing epoxy resin, characterized in that The fluorine-containing epoxy resin is obtained by curing the fluorine-containing monomer according to claim 1 or 2; the curing is curing with a curing agent or UV curing; The molecular weight of the fluorine-containing epoxy resin ranges from 400 to 2000, and the viscosity ranges from 900 mPa·s to 1300 mPa·s; the dielectric constant of the fluorine-containing epoxy resin ranges from 2.3 C² / (N·M²) to 2.8 C² / (N·M²).

14. The fluorine-containing epoxy resin according to claim 13, characterized in that The curing agent is at least one of 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene or hexahydrophthalic anhydride.

15. The fluorine-containing epoxy resin according to claim 13, characterized in that The saturated water absorption rate of the fluorine-containing epoxy resin is 0.8% to 3.2%.

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