CN112538004A - Octafluorocyclopentenyl benzocyclobutene functionalized monomer and preparation and application thereof - Google Patents
Octafluorocyclopentenyl benzocyclobutene functionalized monomer and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to an octafluorocyclopentenyl benzocyclobutene functionalized monomer, and preparation and application thereofThe structure is as follows:
wherein, the R substituent is trifluoromethyl, hydrogen atom, methyl, allyl or propenyl. The monomer is prepared by reacting octafluorocyclopentene with a compound containing benzocyclobutene under the action of a solvent and a catalyst. The monomer can be applied to preparing high-temperature-resistant and low-dielectric polymer materials. Compared with the prior art, the invention has the advantages that the monomer can be post-cured, the high-temperature resistant and low-dielectric polymer material can be obtained after post-curing reaction, side reaction is less in the monomer preparation process, and the like.
Description
Technical Field
The invention relates to the technical field of polymer materials, and particularly relates to an octafluorocyclopentenyl benzocyclobutene functionalized monomer, and preparation and application thereof.
Background
The fluorine-containing polymer material has excellent performances of excellent thermal stability, chemical resistance, low refractive index, low dielectric constant and the like. Octafluorocyclopentene (OFCP) can generate nucleophilic substitution reaction with phenol under mild condition to generate fluorine-containing aryl ether compounds.
Bruce M.Novak, university of Texas, USA, etc. utilizes octafluorocyclopentene to synthesize fluorinated diaminobenzoxazine through nucleophilic substitution reaction, and two kinds of resins are obtained through post-curing. However, the side reactions are more in the reaction process, so that a mono-substituted product (only one F atom in octafluorocyclopentene participates in nucleophilic substitution) is easily obtained, and the dielectric constant of the resin is not low enough and is 3.2-2.6.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an octafluorocyclopentenyl benzocyclobutene functionalized monomer, and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme: an octafluorocyclopentenyl benzocyclobutene functionalized monomer, which has the following structure:
wherein, R substituent is trifluoromethyl, hydrogen atom, methyl, allyl or propenyl, and the monomer is preferably the following structure:
the octafluorocyclopentenyl benzocyclobutene functionalized monomer can generate post-curing reaction to generate a polymer.
The preparation method of the octafluorocyclopentene-based benzocyclobutene functionalized monomer is to react octafluorocyclopentene and a compound containing benzocyclobutene under the action of a solvent and a catalyst to obtain the octafluorocyclopentene-based benzocyclobutene functionalized monomer.
Further, the preparation method of the octafluorocyclopentenyl benzocyclobutene functionalized monomer specifically comprises the following steps:
respectively dissolving octafluorocyclopentene and a compound containing benzocyclobutene in an aprotic polar solvent, adding a catalyst into a solution containing the benzocyclobutene compound, adding an octafluorocyclopentene solution into the solution containing the benzocyclobutene compound, reacting for 1-24 hours at-20-150 ℃, extracting, drying, filtering, concentrating and purifying a product to obtain the monomer.
Furthermore, the mol ratio of the octafluorocyclopentene to the compound containing benzocyclobutene is 1: 2-3, and preferably 1: 2.
The benzocyclobutene-containing compound (MO-BE-BCB) has the following structure:
wherein, R substituent is trifluoromethyl, hydrogen atom, methyl, allyl or propenyl; the M substituent is hydrogen atom, tert-butyl dimethyl silicon base, trimethyl silicon base, triethyl silicon base or triisopropyl silicon base.
The aprotic polar solvent is one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, diethyl ether, 2-methyltetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide and hexamethylphosphoric triamide;
the catalyst is potassium carbonate, triethylamine, sodium carbonate, potassium phosphate, cesium fluoride, cesium carbonate, tetrabutylammonium fluoride, ammonium fluoride or a mixture of cesium carbonate and potassium fluoride;
the reaction temperature is preferably 0-80 ℃, the reaction time is preferably 2-10 h, and the reaction is preferably carried out for 0.5-5 h at 0-20 ℃, and then slowly heated to 50-80 ℃ for reaction for 1-10 h;
the extraction method comprises the steps of extracting for 1-4 times by using one or more solvents of ethyl acetate, petroleum ether, toluene, dichloromethane, trichloromethane, tetrahydrofuran, diethyl ether and 2-methyltetrahydrofuran, drying by using anhydrous magnesium sulfate or anhydrous sodium sulfate, and purifying by using a silica gel column chromatography (a mobile phase is petroleum ether or n-hexane, ethyl acetate or a mixed solvent thereof) or by using a recrystallization method.
When the M substituent is hydrogen atom, the compound containing benzocyclobutene is a (4-hydroxyphenyl) -4-benzocyclobutene compound (HO-BE-BCB), and comprises the following structure:
the compound (HO-BE-BCB) containing benzocyclobutene is synthesized by performing Suzuki reaction on 4-bromobenzocyclobutene and a compound containing phenolic hydroxyl and boric acid or boric acid ester under the action of a palladium series catalyst, wherein the structure of the compound containing phenolic hydroxyl and boric acid or boric acid ester is as follows:
or the compound (HO-BE-BCB) containing the benzocyclobutene is synthesized by performing a suzuki reaction on 4-boratabenzcyclobutane or 4-borate benzocyclobutene and a compound containing phenolic hydroxyl and bromine groups under the action of a palladium-series catalyst.
Typical structures of 4-boronate benzocyclobutene include:
the structure of the compound containing phenolic hydroxyl and bromine is as follows:
wherein R is a substituent on a benzene ring, and is trifluoromethyl, a hydrogen atom, methyl, allyl or propenyl.
The molar ratio of the 4-bromobenzocyclobutene to the compound containing phenolic hydroxyl and boric acid or boric acid ester is 1: 1-2; the molar ratio of the 4-boric acid benzocyclobutene or 4-boric acid ester benzocyclobutene to the compound containing phenolic hydroxyl and bromine is 1: 1-2.
The solvent used in the Suzuki reaction is one or more of tetrahydrofuran, toluene, xylene, dioxane or water; palladium-series catalysts include palladium/carbon, palladium acetate, tetrakis (triphenylphosphine) palladium, palladium dichloride, tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), bis (acetonitrile) palladium (II) dichloride, bis (triphenylphosphine) palladium chloride, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride; the alkali used in the Suzuki reaction process is one or more of potassium acetate, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate and potassium phosphate; the reaction temperature is 50-120 ℃, preferably 60-90 ℃, and the reaction time is 2-48 h, preferably 4-24 h; after the reaction is finished, acidifying the reaction liquid to weak acidity by using dilute hydrochloric acid, extracting an organic phase by using ethyl acetate, diethyl ether or toluene, combining the organic phases, drying, concentrating, and purifying by passing through a column (a stationary phase is silica gel, a mobile phase is petroleum ether, n-hexane, ethyl acetate or a mixed solvent thereof) to obtain the compound containing benzocyclobutene, wherein the M substituent is hydrogen atom.
When the M substituent is tert-butyl dimethyl silicon base, trimethyl silicon base, triethyl silicon base or triisopropyl silicon base, the compound containing benzocyclobutene is prepared by reacting the compound containing benzocyclobutene, the M substituent is hydrogen atom, with chlorosilane in a solvent, an acid binding agent is added in the reaction process, the reaction is washed after the reaction is finished, an organic phase is extracted, the organic phase is dried and then concentrated, and then the silica gel is purified by passing through a column (the mobile phase is petroleum ether, normal hexane, ethyl acetate or a mixed solvent thereof) to obtain the compound containing benzocyclobutene, the M substituent is tert-butyl dimethyl silicon base, trimethyl silicon base, triethyl silicon base or triisopropyl silicon base.
The molar ratio of the benzocyclobutene-containing compound with the M substituent as a hydrogen atom to the chlorosilane is 1: 1-3, and the molar ratio of the acid-binding agent to the chlorosilane is 1: 1-3.
Further, the chlorosilane is tert-butyldimethylchlorosilane, trimethylchlorosilane, triethylchlorosilane or triisopropylchlorosilane; the solvent is tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, acetone, trichloromethane or toluene; the acid-binding agent is imidazole, pyridine, triethylamine, trimethylamine or 2-methylimidazole; the reaction temperature is-30 to 50 ℃, and preferably-20 to 30 ℃; extracting the organic phase with one or more of tetrahydrofuran, petroleum ether, dichloromethane, chloroform, toluene, ethyl acetate, 2-methyltetrahydrofuran, and diethyl ether.
The method adopts a silicon ether protection method to react the benzocyclobutene compound of the phenolic hydroxyl group with the octafluorocyclopentene, so as to avoid the generation of moisture in the reaction process.
The application of the octafluorocyclopentenyl benzocyclobutene functionalized monomer comprises the step of applying the monomer to the preparation of a high-temperature-resistant and low-dielectric polymer film, a polymer block or a high-temperature-resistant composite material.
Further, the specific method for applying the monomer to the preparation of the high-temperature-resistant and low-dielectric polymer film comprises the following steps: dissolving the monomer in a high-boiling-point solvent mesitylene solvent, carrying out nitrogen protection at 150-180 ℃, carrying out prepolymerization for 8-48 h to obtain a prepolymer solution, carrying out spin coating on the prepolymer solution to form a film, heating to 200-300 ℃, and carrying out heating curing to obtain a high-temperature-resistant low-dielectric polymer film;
the specific method for applying the monomer to preparing the high-temperature-resistant low-dielectric polymer block comprises the following steps: and adding the monomer into a mold, heating and melting under the protection of nitrogen, and then curing at 180-260 ℃ for 8-12 h to obtain the high-temperature-resistant low-dielectric polymer block.
The specific method for applying the monomer to the preparation of the high-temperature-resistant composite material comprises the following steps: taking the monomer as a resin matrix, heating and melting the monomer under the protection of nitrogen to realize partial crosslinking of the monomer, then compounding the monomer with carbon fibers, glass fibers, boron fibers, polybenzimidazole fibers, polyimide fibers or polyamide fibers, and performing post-curing to prepare a high-temperature-resistant composite material;
or compounding the monomer with carbon fiber, glass fiber, boron fiber, polybenzimidazole fiber, polyimide fiber or polyamide fiber under the action of a solvent, and performing post-curing to prepare the high-temperature-resistant composite material.
Compared with the prior art, the invention has the following advantages:
1. the monomer has low dielectric constant, can be subjected to postcuring to obtain a polymer with higher thermal stability, higher glass transition temperature, lower dielectric constant (k is less than 2.6) and dielectric loss, and can be used in the fields of chips, electronic packaging, wave-transmitting materials, large-scale integrated circuits and the like;
2. the preparation process of the monomer has less side reaction, and the benzocyclobutene compound of phenolic hydroxyl is reacted with octafluorocyclopentene by adopting a silicon ether protection method, so that the generation of moisture in the reaction process is avoided;
3. the monomer can be applied to preparing high-temperature-resistant low-dielectric polymer films or blocks and also can be applied to preparing high-performance resin composite materials, and the curing mode is simple and various, and the application range is wide.
Drawings
FIG. 1 is a graph of dielectric constant and dielectric loss versus frequency for a polymer material obtained after curing of octafluorocyclopentenyl benzocyclobutene-functionalized monomers in accordance with the present invention;
FIG. 2 shows the BCBOFCP of the present invention1H NMR spectrum;
FIG. 3 shows the BCBOFCP of the present invention19F NMR spectrum.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
Example 1
An octafluorocyclopentenyl benzocyclobutene functionalized monomer BCBOFCP having the structure shown below:
the monomer is a white solid, and the melting point is 85 ℃;
the initial decomposition temperature of the polymer block obtained after the monomer is cured is above 390 ℃, the 5 percent thermal decomposition temperature is about 425 ℃, and the 10 percent decomposition temperature is about 435 ℃; the storage modulus (G') is 1600MPa at room temperature, and the storage modulus is still more than 800MPa at about 150 ℃; glass transition temperature (T)g) Is 210 ℃; in the range of 10k-1MHz, has low dielectric constant (k is about 2.6) and dielectric loss (<0.002)。
Example 2
A method for preparing octafluorocyclopentenyl benzocyclobutene functionalized monomer comprises the following steps:
the first step is as follows: preparation of benzocyclobutene (BCB) derivative (4-hydroxyphenyl) -4' -benzocyclobutene (HO-BE-BCB-H).
4-Hydroxyphenylboronic acid (2.76g, 0.02mol), 4-bromobenzocyclobutene (3.66g, 0.02mol), tetrakis (triphenylphosphine) palladium (0.1g), potassium carbonate (4.14g, 0.003mol), 30mL dioxane, and 25mL deionized water were added to a 100mL round bottom flask equipped with a condenser and a stir bar, equipped with a nitrogen-filled balloon over the system, and the nitrogen was replaced three times. The reaction is carried out for 10h at 80 ℃. Filtering after the reaction is finished, repeatedly extracting the filtrate for three times by using ethyl acetate, then carrying out rotary evaporation and concentration, purifying the concentrated solution by using column chromatography (ethyl acetate: petroleum ether: 1:6), and drying the concentrated solution in a vacuum oven at 80 ℃ overnight to obtain a product HO-BE-BCB-H3.08 g with the yield of 78.6%.
1H NMR(500MHz,DMSO-d6,δ,ppm):9.46(s,1H),7.39(d,2H),7.35(dd,1H),7.24(d,1H),7.09(d,1H),6.85–6.77(m,2H),3.14(s,4H)。
The second step is that: and preparing the TDMS-BE-BCB-H by the silyl ether protection of HO-BE-BCB-H.
HO-BE-BCB-H (1.96g, 0.01mol), t-butyldimethylchlorosilane (4.52g, 0.03mol), imidazole (2.04g, 0.03mol), and 40mL of tetrahydrofuran were charged into a 100mL single-neck flask equipped with a condenser tube, and the system was protected with nitrogen using a balloon filled with nitrogen. Reflux reaction for 10h, after the reaction is finished, filtering, adding 20mL deionized water into the filtrate, repeatedly extracting with petroleum ether for 3 times (20mL x 3), combining organic phases, drying with anhydrous magnesium sulfate, concentrating the filtrate with a rotary evaporator after filtering, and separating the concentrated solution by column chromatography (pure petroleum ether) to obtain 2.95g of white solid (yield: 95.2%).
1H NMR(400MHz,CDCl3,δ,ppm):7.45(d,2H),7.35(d,1H),7.11(d,1H),6.91(d,2H),3.23(s,4H),1.03(s,9H),0.25(s,1H)。
13C NMR(101MHz,CDCl3,δppm):154.96,146.13,144.30,140.13,135.56,128.23,125.79,122.69,121.26,120.24,29.37,25.76,-4.33。
28Si NMR(99MHz,CDCl3,δ,ppm):20.36。
The third step: preparation of octafluorocyclopentenyl BCB monomer (BCBOFCP-H).
TDMS-BE-BCB-H (1.55g, 5mmol), 20mL of N-methylpyrrolidone (NMP), cesium fluoride (CsF) (0.1g) were charged into a 25mL two-necked flask equipped with a dropping funnel, and the other end of the flask was protected with a nitrogen balloon. The solution of octafluorocyclopentene (0.53g, 2.5mmol) in NMP (5mL) was added to the dropping funnel, the system was placed in an ice bath, and while stirring, the octafluorocyclopentene solution was added dropwise, after 2 hours, the dropwise addition was completed, and the reaction was continued at 0 ℃ for 8 hours. After the reaction was completed, 15mL of deionized water was added to the reaction system, followed by extraction 3 times (10mL × 3) with petroleum ether, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator. The concentrated solution was separated by column chromatography (pure petroleum ether) to obtain 1.02g of a white solid (yield: 72.3%).
1H NMR(400MHz,Chloroform-d,δ,ppm):7.28(d,4H),7.26(d,2H),7.13(s,2H),7.11(d,2H),6.83–6.58(m,2H),3.33(m,8H)。
19F NMR(376MHz,Chloroform-d,δ,ppm):-113.27(d,J＝4.9Hz,4F),-128.80(s,2F)。
Example 3
A preparation method of octafluorocyclopentenyl benzocyclobutene functionalized monomer comprises the following steps:
HO-BE-BCB-H (0.98g, 5mmol), 20mL of NMP, and potassium carbonate (0.69g) were charged into a 25mL two-necked flask equipped with a dropping funnel, and the other end of the flask was protected with a nitrogen balloon. The solution of octafluorocyclopentene (0.53g, 2.5mmol) in NMP (5mL) was added to the dropping funnel, the system was placed in an ice bath, and while stirring, the octafluorocyclopentene solution was added dropwise, after 2 hours, the dropwise addition was completed, and the reaction was continued at 0 ℃ for 8 hours. After the reaction was completed, 15mL of deionized water was added to the reaction system, followed by extraction 3 times (10mL × 3) with petroleum ether, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator. The concentrated solution was separated by column chromatography (pure petroleum ether) to obtain 0.54g of a white solid (yield: 38.5%).
Example 4
An octafluorocyclopentenyl benzocyclobutene functionalized monomer,
the preparation process comprises the following steps:
the first step is as follows: preparation of benzocyclobutene (BCB) derivative (3-trifluoromethyl-4-hydroxyphenyl) -4' -benzocyclobutene (HO-BE-BCB-CF).
3-trifluoromethyl-4-hydroxyphenylboronic acid (4.118g, 0.02mol), 4-bromobenzocyclobutene (3.66g, 0.02mol), tetrakis (triphenylphosphine) palladium (0.1g), potassium carbonate (4.14g, 0.003mol), 30mL dioxane, and 25mL deionized water were added to a 100mL round bottom flask equipped with a condenser and a stir bar, equipped with a nitrogen-filled balloon over the system, and the nitrogen was replaced three times. The reaction is carried out for 10h at 80 ℃. Filtering after the reaction is finished, repeatedly extracting the filtrate for three times by using ethyl acetate, then carrying out rotary evaporation and concentration, purifying the concentrated solution by using column chromatography (ethyl acetate: petroleum ether: 1:7), and drying the concentrated solution in a vacuum oven at 80 ℃ overnight to obtain 4.12g of a product HO-BE-BCB-CF with the yield of 78.0%.
1H NMR(500MHz,DMSO-d6,δ,ppm):9.52(s,1H),7.86(s,1H),7.58(d,1H),7.39(s,1H),7.35(d,1H),7.24(d,1H),6.93(d,1H),3.16(s,4H)。
The second step is that: HO-BE-BCB-CF (1.32g, 5mmol), 20mL of NMP, and potassium carbonate (0.69g) were charged into a 25mL two-necked flask equipped with a dropping funnel, and the other end of the flask was protected with a nitrogen balloon. The solution of octafluorocyclopentene (0.53g, 2.5mmol) in NMP (5mL) was added to the dropping funnel, the system was placed in an ice bath, and while stirring, the octafluorocyclopentene solution was added dropwise, after 2 hours, the dropwise addition was completed, and the reaction was continued at 0 ℃ for 8 hours. After the reaction was completed, 15mL of deionized water was added to the reaction system, followed by extraction 3 times (10mL × 3) with petroleum ether, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator. The concentrated solution was separated by column chromatography (pure petroleum ether) to obtain 0.72g of a white solid (yield: 41.1%).
1H NMR(400MHz,Chloroform-d,δ,ppm):7.85(s,2H),7.62(d,2H),7.30(d,2H),7.38(s,2H),7.26(d,2H),6.96(d,2H),3.28(m,8H)。
19F NMR(376MHz,Chloroform-d,δ,ppm):-113.27(d,4F),-128.80(s,2F),-63.52(s,6H)。
Example 5
An octafluorocyclopentenyl benzocyclobutene functionalized monomer,
the preparation process comprises the following steps:
the first step is as follows: preparation of benzocyclobutene (BCB) derivative (3-methyl-4-hydroxyphenyl) -4' -benzocyclobutene (HO-BE-BCB-Me).
3-methyl-4-hydroxyphenylboronic acid (3.04g, 0.02mol), 4-bromobenzocyclobutene (3.66g, 0.02mol), tetrakis (triphenylphosphine) palladium (0.1g), potassium carbonate (4.14g, 0.003mol), 30mL dioxane, 25mL deionized water were added to a 100mL round bottom flask equipped with a condenser and a stir bar, and a nitrogen-filled balloon was placed over the system and the nitrogen was replaced three times. The reaction is carried out for 10h at 80 ℃. Filtering after the reaction is finished, repeatedly extracting the filtrate for three times by using ethyl acetate, then carrying out rotary evaporation and concentration, purifying the concentrated solution by using column chromatography (ethyl acetate: petroleum ether: 1:7), and drying the concentrated solution in a vacuum oven at 80 ℃ overnight to obtain 2.90g of a product HO-BE-BCB-Me, wherein the yield is 69.1%.
1H NMR(500MHz,DMSO-d6,δ,ppm):9.68(s,1H),7.52(s,1H),7.39(s,1H),7.35(d,1H),7.30(d,1H),7.24(d,1H),6.86(d,1H),3.16(s,4H)，2.23(s,3H)。
The second step is that: HO-BE-BCB-Me (1.05g, 5mmol), 20mL of NMP, and potassium carbonate (0.69g) were charged into a 25mL two-necked flask equipped with a dropping funnel, and the other end of the flask was protected with a nitrogen balloon. The solution of octafluorocyclopentene (0.53g, 2.5mmol) in NMP (5mL) was added to the dropping funnel, the system was placed in an ice bath, and while stirring, the octafluorocyclopentene solution was added dropwise, after 2 hours, the dropwise addition was completed, and the reaction was continued at 0 ℃ for 8 hours. After the reaction was completed, 15mL of deionized water was added to the reaction system, followed by extraction 3 times (10mL × 3) with petroleum ether, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator. The concentrated solution was separated by column chromatography (pure petroleum ether) to obtain 0.597g of a white solid (yield: 40.3%).
1H NMR(400MHz,Chloroform-d,δ,ppm):7.50(s,2H),7.38(d,2H),7.33(s,2H),7.30(d,2H),7.27(d,2H),6.88(d,2H),3.28(m,8H)，2.25(s,6H)。
19F NMR(376MHz,Chloroform-d,δ,ppm):-113.56(d,4F),-128.32(s,2F)。
Example 6
An octafluorocyclopentenyl benzocyclobutene functionalized monomer,
the preparation process comprises the following steps:
the first step is as follows: preparation of benzocyclobutene (BCB) derivative (3-allyl-4-hydroxyphenyl) -4' -benzocyclobutene (HO-BE-BCB-Al).
3-allyl-4-hydroxybenzene (4.26g, 0.02mol), 4-pinacolboronic acid ester benzocyclobutene (3.66g, 0.02mol), tetrakis (triphenylphosphine) palladium (0.1g), potassium carbonate (4.14g, 0.003mol), 30mL dioxane, 25mL deionized water were added to a 100mL round bottom flask equipped with a condenser and a stir bar, and a nitrogen-filled balloon was placed over the system and the nitrogen was replaced three times. The reaction is carried out for 10h at 80 ℃. Filtering after the reaction is finished, repeatedly extracting the filtrate for three times by using ethyl acetate, then carrying out rotary evaporation and concentration, purifying the concentrated solution by using column chromatography (ethyl acetate: petroleum ether: 1:7), and drying the concentrated solution in a vacuum oven at 80 ℃ overnight to obtain 2.99g of a product HO-BE-BCB-Al, wherein the yield is 63.5%.
1H NMR(500MHz,DMSO-d6,δ,ppm):9.68(s,1H),7.52(s,1H),7.39(s,1H),7.35(d,1H),7.30(d,1H),7.24(d,1H),6.86(d,1H),3.16(s,4H)，5.86(dd,1H),5.03(dd，1H),4.86(dd,1H),2.23(s,3H)。
The second step is that: HO-BE-BCB-Al (1.18g, 5mmol), 20mL of NMP, and potassium carbonate (0.69g) were charged into a 25mL two-necked flask equipped with a dropping funnel, and the other end of the flask was protected with a nitrogen balloon. The solution of octafluorocyclopentene (0.53g, 2.5mmol) in NMP (5mL) was added to the dropping funnel, the system was placed in an ice bath, and while stirring, the octafluorocyclopentene solution was added dropwise, after 2 hours, the dropwise addition was completed, and the reaction was continued at 0 ℃ for 8 hours. After the reaction was completed, 15mL of deionized water was added to the reaction system, followed by extraction 3 times (10mL × 3) with petroleum ether, and the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by a rotary evaporator. The concentrated solution was separated by column chromatography (pure petroleum ether) to obtain 0.696g of a white solid (yield: 43.2%).
1H NMR(400MHz,Chloroform-d,δ,ppm):7.50(s,2H),7.38(d,2H),7.33(s,2H),7.30(d,2H),7.27(d,2H),6.88(d,2H),5.86(dd,2H),5.03(dd,2H),4.86(dd,2H),3.28(m,8H)，2.25(s,6H)。
19F NMR(376MHz,Chloroform-d,δ,ppm):-113.8(d,4F),-128.9(s,2F)。
Example 7
The application of octafluorocyclopentenyl benzocyclobutene functionalized monomer is to prepare a polymer block material by post-curing the monomer.
The specific method comprises the following steps: adding a certain mass of BCBOFCP into a square quartz mold of 2cm x 2cm, horizontally placing in a tube furnace, and respectively keeping the temperature at 120 ℃ for 1h (ensuring uniform distribution and bubble removal after melting), at 180 ℃ for 2h, at 200 ℃ for 2h, at 220 ℃ for 2h, at 240 ℃ for 2h and at 260 ℃ for 2h under the nitrogen atmosphere. After curing was complete, the block was edge ground to give a 2cm by 0.75mm pale yellow block having a dielectric constant of 2.57, an initial decomposition temperature of 425 ℃ and a glass transition temperature of 210 ℃.
Example 8
An application of octafluorocyclopentenyl benzocyclobutene functionalized monomer is to prepare a high-temperature-resistant composite material by compounding the monomer and glass fiber.
The specific method comprises the following steps: heating and melting the octafluorocyclopentenyl benzocyclobutene functionalized monomer under the protection of nitrogen to realize partial crosslinking of the monomer, then compounding the monomer with glass fiber, and performing post-curing to prepare the high-temperature-resistant composite material, wherein the dielectric constant of the obtained composite material is 3.05, and the initial decomposition temperature is 445 ℃.
Example 9
The application of octafluorocyclopentenyl benzocyclobutene functionalized monomer is to apply the monomer to the preparation of a high-temperature-resistant low-dielectric polymer film.
The specific method comprises the following steps: the monomer is pre-polymerized for 24 hours in a high-boiling point solvent mesitylene solvent at 160 ℃ under the protection of nitrogen to obtain a pre-polymer solution, the pre-polymer solution is spin-coated to form a film, the film is heated to 250 ℃ and heated and cured to obtain a high-temperature-resistant low-dielectric polymer film, the dielectric constant of the obtained polymer film is 2.57, the initial decomposition temperature is 425 ℃, and the glass transition temperature is 210 ℃.
Example 10
A method for preparing octafluorocyclopentenyl benzocyclobutene functionalized monomer comprises the following steps:
adding 4-benzocyclobutene borate, a compound containing phenolic hydroxyl and bromo, palladium acetate, sodium carbonate and tetrahydrofuran into a round-bottom flask provided with a condenser tube and a stirrer, arranging a balloon filled with nitrogen above a system, replacing the nitrogen for three times, reacting for 2-48 h at 50-120 ℃, adding dilute hydrochloric acid after the reaction is finished, acidifying to weak acidity, filtering, repeatedly extracting the filtrate for three times by using ethyl acetate, performing rotary evaporation and concentration, purifying the concentrated solution by column chromatography (ethyl acetate: petroleum ether ═ 1:6), and drying overnight in a vacuum oven at 80 ℃ to obtain a product (4-hydroxyphenyl) -4-benzocyclobutene compound, wherein the reaction formula is as follows:
and secondly, adding the product obtained in the first step, trimethylchlorosilane, pyridine and dichloromethane into a single-neck flask provided with a condenser tube, and carrying out nitrogen protection on the system by using a balloon filled with nitrogen. Carrying out reflux reaction at-30-50 ℃ overnight, after the reaction is finished, washing with water, filtering, repeatedly extracting with ethyl acetate for three times (20mL by 3), combining organic phases, drying with anhydrous magnesium sulfate, concentrating the organic phase with a rotary evaporator, purifying the concentrated solution with column chromatography (pure petroleum ether) to obtain a compound containing benzocyclobutene, wherein the hydrogen atom of the compound is replaced by trimethylsilyl, and the reaction formula is as follows:
and thirdly, adding the product obtained in the second step, ethylene glycol diethyl ether and potassium carbonate into a two-neck flask provided with a dropping funnel, protecting the other end of the flask by using a nitrogen ball, adding an ethylene glycol diethyl ether solution of octafluorocyclopentene into the dropping funnel, dropwise adding the octafluorocyclopentene solution while stirring, reacting at the temperature of-20-150 ℃ for 1-24 hours after dropwise adding is finished, distilling under reduced pressure to remove the solvent after the reaction is finished, pouring the product into water, extracting twice (10 mL) with ethyl acetate, combining organic phases, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate by using a rotary evaporator, and purifying the concentrated solution by using column chromatography (pure petroleum ether) to obtain the octafluorocyclopentene benzocyclobutene functionalized monomer.
Example 11
A method for preparing octafluorocyclopentenyl benzocyclobutene functionalized monomer comprises the following steps:
adding 4-borate benzocyclobutene, a compound containing phenolic hydroxyl and bromo, bis (dibenzylideneacetone) palladium (0), potassium phosphate and xylene into a round-bottom flask provided with a condenser tube and a stirrer, arranging a balloon filled with nitrogen above a system, displacing the nitrogen for three times, reacting for 4-24 hours at 60-90 ℃, filtering, repeatedly extracting the filtrate for three times by using diethyl ether, performing rotary evaporation and concentration, purifying the concentrated solution by using column chromatography (ethyl acetate: petroleum ether ═ 1:6), and drying overnight in a vacuum oven at 80 ℃ to obtain a product (4-hydroxyphenyl) -4-benzocyclobutene compound;
and secondly, adding the product obtained in the first step, triisopropylchlorosilane, triethylamine and toluene into a single-neck flask provided with a condenser tube, and performing nitrogen protection on the system by using a balloon filled with nitrogen. Carrying out reflux reaction at the temperature of-20-30 ℃ overnight, after the reaction is finished, washing with water, filtering, repeatedly extracting with a mixed solution of tetrahydrofuran and diethyl ether for three times (20mL × 3), combining organic phases, drying with anhydrous magnesium sulfate, concentrating the organic phases by using a rotary evaporator, and purifying the concentrated solution by using column chromatography (pure petroleum ether) to obtain a compound containing benzocyclobutene, wherein hydrogen atoms of the compound are replaced by triisopropylsilyl;
and thirdly, adding the product obtained in the second step, dimethyl sulfoxide and tetrabutylammonium fluoride into a two-neck flask provided with a dropping funnel, protecting the other end of the flask by using a nitrogen ball, adding a dimethyl sulfoxide solution of octafluorocyclopentene into the dropping funnel, dropwise adding the octafluorocyclopentene solution while stirring, reacting at 0-20 ℃ for 0.5-5 h after dropwise adding, slowly heating to 50-80 ℃ for reacting for 1-10 h, removing the solvent by reduced pressure distillation after the reaction is finished, pouring the product into water, extracting with 2-methyltetrahydrofuran for four times (10mL 4), combining organic phases, drying with anhydrous calcium chloride, filtering, concentrating the filtrate by using a rotary evaporator, and recrystallizing the concentrated solution to obtain the octafluorocyclopentene benzocyclobutene functionalized monomer.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. An octafluorocyclopentenyl benzocyclobutene functionalized monomer, characterized by having the structure shown below:
wherein, the R substituent is trifluoromethyl, hydrogen atom, methyl, allyl or propenyl.
2. A process for the preparation of octafluorocyclopentenyl benzocyclobutene functionalized monomer according to claim 1, characterized in that octafluorocyclopentene and a benzocyclobutene-containing compound are reacted in the presence of a solvent and a catalyst to obtain said monomer.
3. The method of claim 2 wherein said benzocyclobutene-containing compound has the structure:
wherein, R substituent is trifluoromethyl, hydrogen atom, methyl, allyl or propenyl; the M substituent is hydrogen atom, tert-butyl dimethyl silicon base, trimethyl silicon base, triethyl silicon base or triisopropyl silicon base.
4. The method of claim 3, comprising the steps of: respectively dissolving octafluorocyclopentene and a compound containing benzocyclobutene in an aprotic polar solvent, adding a catalyst into a solution containing the benzocyclobutene compound, adding an octafluorocyclopentene solution into the solution containing the benzocyclobutene compound, reacting for 1-24 hours at-20-150 ℃, extracting, drying, filtering, concentrating and purifying a product to obtain the monomer.
5. The method for preparing octafluorocyclopentenyl benzocyclobutene functionalized monomer according to claim 4, wherein the molar ratio of octafluorocyclopentene to benzocyclobutene-containing compound is 1: 2-3, and the aprotic polar solvent is one or more of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, N-dimethylformamide, N-dimethylacetamide, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide and hexamethylphosphoric triamide;
the catalyst is potassium carbonate, triethylamine, sodium carbonate, potassium phosphate, cesium fluoride, cesium carbonate, tetrabutylammonium fluoride, ammonium fluoride or a mixture of cesium carbonate and potassium fluoride;
the reaction process comprises the steps of firstly reacting for 0.5-5 h at 0-20 ℃, and then slowly heating to 50-80 ℃ for reacting for 1-10 h;
the extraction method comprises the steps of extracting for 1-4 times by using one or more of ethyl acetate, tetrahydrofuran, diethyl ether, petroleum ether, toluene, dichloromethane, trichloromethane and 2-methyltetrahydrofuran, drying by using anhydrous magnesium sulfate, anhydrous sodium sulfate or anhydrous calcium chloride, and purifying by using column chromatography or recrystallization.
6. The method for preparing octafluorocyclopentenyl benzocyclobutene functional monomers according to claim 3, characterized in that the M substituent in the benzocyclobutene-containing compound is a hydrogen atom, and the synthesis is carried out by a suzuki reaction using 4-bromobenzocyclobutene and a compound containing a phenolic hydroxyl group and boric acid or a boric acid ester in the presence of a palladium-based catalyst;
or 4-boric acid benzocyclobutene or 4-boric acid ester benzocyclobutene and a compound containing phenolic hydroxyl and bromine groups are used for performing suzuki reaction synthesis under the action of a palladium catalyst.
7. The method of claim 6 wherein the compound containing a phenolic hydroxyl group and a boronic acid or ester has the structure:
the structure of the compound containing phenolic hydroxyl and bromine is as follows:
the structure of the 4-borate benzocyclobutene comprises:
wherein R is trifluoromethyl, hydrogen atom, methyl, allyl or propenyl; the molar ratio of the 4-bromobenzocyclobutene to the compound containing phenolic hydroxyl and boric acid or boric acid ester is 1: 1-2; the molar ratio of the 4-boric acid benzocyclobutene or 4-boric acid ester benzocyclobutene to the compound containing phenolic hydroxyl and bromine is 1: 1-2;
the solvent used in the Suzuki reaction is one or more of tetrahydrofuran, toluene, xylene, dioxane or water; palladium-series catalysts include palladium/carbon, palladium acetate, tetrakis (triphenylphosphine) palladium, palladium dichloride, tris (dibenzylideneacetone) dipalladium (0), bis (dibenzylideneacetone) palladium (0), bis (acetonitrile) palladium (II) dichloride, bis (triphenylphosphine) palladium chloride, [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride; the alkali used in the Suzuki reaction process is one or more of potassium acetate, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate and potassium phosphate; the reaction temperature is 50-120 ℃, and the reaction time is 2-48 h; extracting the organic phase with ethyl acetate, diethyl ether or toluene, mixing the organic phases, drying, concentrating, and purifying with column chromatography to obtain benzocyclobutene-containing compound with M substituent as hydrogen atom.
8. The method for preparing octafluorocyclopentenyl benzocyclobutene functionalized monomer according to claim 3, wherein the M substituent in the benzocyclobutene-containing compound is tert-butyldimethylsilyl, trimethylsilyl, triethylsilyl or triisopropylsilyl, and the benzocyclobutene-containing compound is prepared by reacting a benzocyclobutene-containing compound in which the M substituent is a hydrogen atom with chlorosilane in a solvent, adding an acid-binding agent during the reaction, washing with water after the reaction is finished, extracting an organic phase, drying the organic phase, concentrating, and purifying by passing through a column to obtain a benzocyclobutene-containing compound in which the M substituent is tert-butyldimethylsilyl, trimethylsilyl, triethylsilyl or triisopropylsilyl;
the molar ratio of the benzocyclobutene-containing compound with the M substituent as a hydrogen atom to the chlorosilane is 1: 1-3, and the molar ratio of the acid-binding agent to the chlorosilane is 1: 1-3.
9. The method of preparing an octafluorocyclopentenylbenzocyclobutene-functional monomer according to claim 8, characterized in that the chlorosilane is t-butyldimethylsilyl chloride, trimethylchlorosilane, triethylchlorosilane or triisopropylchlorosilane; the solvent is tetrahydrofuran, 2-methyltetrahydrofuran, dichloromethane, acetone, trichloromethane or toluene; the acid-binding agent is imidazole, pyridine, triethylamine, trimethylamine or 2-methylimidazole; the reaction temperature is-30 to 50 ℃; extracting the organic phase with one or more of tetrahydrofuran, 2-methyltetrahydrofuran, petroleum ether, dichloromethane, chloroform, toluene, ethyl acetate, and diethyl ether.
10. Use of an octafluorocyclopentenyl benzocyclobutene functionalized monomer according to claim 1, wherein the monomer is used for preparing a high temperature resistant, low dielectric polymer film, polymer block or high temperature resistant composite material.
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| CN113831227A (en) * | 2021-10-28 | 2021-12-24 | 中国林业科学研究院林产化学工业研究所 | F-containing binary rosin-based benzocyclobutene monomer and preparation method and application thereof |
| CN115322217A (en) * | 2022-08-11 | 2022-11-11 | 中国科学院化学研究所 | High-refractive-index polymerizable monomer for liquid crystal display light path adjusting coating and preparation method thereof |
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| CN115322217A (en) * | 2022-08-11 | 2022-11-11 | 中国科学院化学研究所 | High-refractive-index polymerizable monomer for liquid crystal display light path adjusting coating and preparation method thereof |
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