CN114106338A - Silicon aryne resin with p-diacetylene diphenylmethane structure and composite material and preparation method thereof - Google Patents

Silicon aryne resin with p-diacetylene diphenylmethane structure and composite material and preparation method thereof Download PDF

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CN114106338A
CN114106338A CN202111231862.1A CN202111231862A CN114106338A CN 114106338 A CN114106338 A CN 114106338A CN 202111231862 A CN202111231862 A CN 202111231862A CN 114106338 A CN114106338 A CN 114106338A
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diphenylmethane
resin
diacetylene
silicon
aryne resin
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黄发荣
袁荞龙
唐均坤
钱建华
江邦和
刘晓天
黎记显
李传
乔志瑶
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
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    • C08K7/04—Fibres or whiskers inorganic
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Abstract

The invention relates to a silicon aryne resin with a p-diacetylene diphenylmethane structure, a composite material thereof and a preparation method thereof. The structural formula is as follows:
Figure DDA0003316305790000011
wherein R is1，R2，R3is-CH3Or H; r is methyl or phenyl; n is an integer of 1 to 5. The resin is solid at normal temperature, the introduction of the side methyl group enables the resin to have better processing performance, the resin can be dissolved in common solvents and can be cured at 170-250 ℃, the bending strength of the cured resin is 42.1MPa, and the dielectric constant is 1-107Less than 3 in the Hz range.0, thermal decomposition temperature Td5It reaches 522 ℃. The bending strength of the T300 carbon fiber reinforced composite material is 381.9MPa, and the bending strength of the composite material is 227.5MPa at 400 ℃. The resin and the composite material thereof have excellent mechanical property and heat resistance, and can be used in the high-tech fields of aerospace and the like.

Description

Silicon aryne resin with p-diacetylene diphenylmethane structure and composite material and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, organic synthesis and composite materials, in particular to silicon aryne resin with a p-diacetylene diphenylmethane structure, a composite material and a preparation method thereof.
Background
The silicon-containing aryne (PSA) resin is an organic-inorganic hybrid thermosetting resin with excellent comprehensive performance, and a condensate of the resin is a highly cross-linked rigid molecular structure, so that the resin has excellent thermal stability and can be used for a high-performance composite material matrix. But also due to the highly crosslinked rigid molecular structure, the silicon-containing aryne resin is brittle and has insufficient mechanical strength, which limits the wide application of the silicon-containing aryne resin in the field of aerospace.
Since 2002, the university of eastern China has developed the basic theory and application research of silicon-containing aryne resin, and from the structure and performance, a series of silicon-containing aryne resins with excellent performance (Huangfa Rong, etc., high temperature resistant aryne resin and its composite material, scientific publishing company, 2020) have been researched and invented. Chen et al introduce aryl ether structure into main chain to improve the mechanical property of silicon-containing aryne resin [ Chen H G, et al. high performance polymers, 2017, 29, 595-601 ]; nickey et al used methyl phenyl dichlorosilane and aryl ether aryne to synthesize silicon-containing aryne resin, and improved the processability of the resin [ nickey et al, proceedings of aeronautical materials, 2019, 39, 69-74 ]; malanping et al introduced heterocyclic ring into the main chain structure of resin to obtain silicon-containing aryne resin [ MaM P, et al RSC advance, 2021, 11, 19656-19665] with excellent mechanical properties.
However, the prior art still lacks of silicon-containing aryne resin which simultaneously has excellent mechanical property, heat resistance and processability.
Disclosure of Invention
Based on the current situation that silicon-containing aryne resin with excellent mechanical property, heat resistance and processability is lacked in the prior art, the invention provides silicon aryne resin with a p-diacetylene diphenylmethane structure, a composite material thereof and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention firstly provides a kind of silicon aryne resin with a structure of p-diacetylene diphenylmethane, which has the following structural formula:
Figure BDA0003316305780000021
wherein R is1、R2、R3Free selection of CH3Or H, R is methyl or phenyl, and n is an integer of 1 to 5.
In one embodiment of the present invention, preferably, n is 2 or 3.
In one embodiment of the present invention, preferably, R1、R2And R3The method comprises the following steps:
1)R1＝R2＝R3h; or the like, or, alternatively,
2)R1＝R2＝-CH3，R3h; or the like, or, alternatively,
3)R1＝H，R2＝R3＝-CH3(ii) a Or the like, or, alternatively,
4)R1＝-CH3，R2＝R3h; or the like, or, alternatively,
5)R1＝R2＝H，R3＝-CH3。
in one embodiment of the present invention, the number average molecular weight of the silicon aryne resin having a p-diacetylene diphenylmethane structure is 900 to 2500, preferably 1200 to 2000; the polydispersity is 1.2 to 1.8, preferably 1.3 to 1.6.
The invention also provides a synthetic method of the silicon aryne resin with the structure of the p-diacetylene diphenylmethane, which comprises the following steps:
1) synthesis of p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with pendant methyl group
11) Dropwise adding sodium nitrite aqueous solution into diaminodiphenylmethane or homologues thereof under an acidic condition to prepare a diazonium salt solution;
12) dripping the diazonium salt solution into potassium iodide (KI) solution, extracting with a solvent after reaction, washing again, drying to remove the solvent, and recrystallizing to obtain p-diiododiphenylmethane or p-diiododiphenylmethane with lateral methyl;
13) adding triethylamine, tetrahydrofuran, trimethylethynylene silane, cuprous iodide and a palladium catalyst into diiododiphenylmethane or diiododiphenylmethane with lateral methyl, carrying out Sonogashira reaction in a nitrogen environment, and washing to obtain a product after the reaction to obtain p-bis (trimethylsilylethynyl) diphenylmethane or p-bis (trimethylsilylethynyl) diphenylmethane with lateral methyl;
14) adding p-bis (trimethylsilylethynyl) diphenylmethane or p-bis (trimethylsilylethynyl) diphenylmethane with a side methyl group into a mixed solvent of methanol and tetrahydrofuran, adding alkali, reacting, removing trimethylsilane, and recrystallizing to obtain p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with a side methyl group;
2) synthesis of resins
21) Under the atmosphere of nitrogen, dropwise adding ethyl bromide into a mixture of magnesium powder and tetrahydrofuran, and reacting to prepare an ethyl Grignard reagent;
22) reacting p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with side methyl in an ethyl Grignard reagent to prepare an alkynyl Grignard reagent;
23) cooling the obtained alkynyl Grignard reagent to below 20 ℃, dropwise adding dichlorosilane, and carrying out polymerization reaction to obtain a polymerization product;
24) adding a solvent into the polymerization product obtained in the step 23) for extraction, after the reaction liquid is cooled to below room temperature, sequentially dropwise adding glacial acetic acid and hydrochloric acid solution to stop the reaction, removing unreacted magnesium powder, washing the extracting solution with water to be neutral, drying, and removing the solvent to obtain the resin.
In one embodiment of the present invention, in step 11), the chemical formula of the diaminodiphenylmethane or a homologue thereof is as follows:
Figure BDA0003316305780000031
wherein R is1、R2、R3Free selection of CH3Or H. Preferably, R1、R2And R3The method comprises the following steps:
1)R1＝R2＝-CH3，R3h; or 2) R1＝H，R2＝R3＝-CH3(ii) a Or 3) R1＝-CH3，R2＝R3H; or 4) R1＝R2＝H，R3＝-CH3。
In one embodiment of the present invention, in step 11), the acidic environment is obtained by one or more of nitric acid, hydrochloric acid, sulfuric acid or acetic acid, preferably hydrochloric acid or sulfuric acid. The concentration of the acid is 10-50%, preferably 30%.
In one embodiment of the present invention, in step 11), the concentration of the sodium nitrite solution is 20% to 35%, preferably 30%.
In one embodiment of the present invention, in step 11), the dropping time of the sodium nitrite solution is10 min to 60min, preferably 15 min.
In one embodiment of the present invention, in step 11), the temperature at which the sodium nitrite solution is dropwise added is controlled to be-20 ℃ to 10 ℃, preferably 0 ℃.
In one embodiment of the invention, in step 11), the molar ratio of sodium nitrite to diaminodiphenylmethane or a homologue thereof is 2.2: 1.0.
In one embodiment of the present invention, in step 12), the diazonium salt solution is dropped into the potassium iodide solution under the reaction conditions: reacting at room temperature for 24h or more.
In one embodiment of the present invention, in step 12), the solvent selected is one of toluene, ethyl acetate or dichloromethane, preferably dichloromethane.
In one embodiment of the invention, in step 12), washing with an aqueous sodium sulfite solution and an aqueous sodium carbonate solution, respectively, is carried out.
In one embodiment of the present invention, in step 12), the solvent selected for recrystallization is 75-99% ethanol aqueous solution, preferably 95% ethanol aqueous solution.
In one embodiment of the invention, in step 12) the molar ratio of potassium iodide to diaminodiphenylmethane or a homologue thereof is 2.5: 1.0.
In one embodiment of the present invention, in step 13), the selected palladium catalyst is one or more of bis-triphenylphosphine palladium dichloride or tetratriphenylphosphine palladium, preferably bis-triphenylphosphine palladium dichloride.
In one embodiment of the invention, copper iodide and palladium iodide catalysts are used as catalysts in step 13), both in 1% molar equivalents.
In the step 13), triethylamine is used as an acid-binding agent and a solvent, and tetrahydrofuran is added to increase the solubility. Therefore, in the implementation of the scheme of the application, quantitative requirements on triethylamine and tetrahydrofuran are not required, and the triethylamine and the tetrahydrofuran can be dissolved. In some embodiments of the present invention, step 13) is carried out in an amount generally required to be at least 2 times greater than the molar amount of p-diiododiphenylmethane or p-diiododiphenylmethane having a pendant methyl group, preferably 10 times greater than the molar amount of p-diiododiphenylmethane or p-diiododiphenylmethane having a pendant methyl group.
In one embodiment of the present invention, in step 13), the Sonogashira reaction is carried out under the following conditions: after the reaction is carried out for 16 hours at 30-70 ℃, the reaction temperature is preferably 40 ℃.
In one embodiment of the present invention, in step 13), after the Sonogashira reaction is performed, filtration is performed to obtain a filtrate, and the solvent in the filtrate is removed and then washing is performed.
In one embodiment of the invention, in step 13), the product is obtained by washing with ethanol or acetonitrile to white or light yellow.
In one embodiment of the present invention, in step 13), the molar ratio of p-diiododiphenylmethane or p-diiododiphenylmethane having a pendant methyl group to trimethylethynylsilane is 1.0: 2.5.
In one embodiment of the present invention, in step 14), the volume ratio of methanol to tetrahydrofuran is 1:2 to 2:1, preferably 1: 1.
In one embodiment of the present invention, in step 14), the base is one or more of sodium hydroxide, potassium hydroxide and potassium carbonate, preferably potassium carbonate.
In one embodiment of the present invention, the removal of trimethylsilane in step 14) is performed at 30 to 65 ℃.
In one embodiment of the present invention, in step 14), the solvent is removed, and then the mixture is thermally extracted with petroleum ether, and recrystallized to obtain p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with a pendant methyl group.
In one embodiment of the present invention, in step 14), the solvent used for recrystallization is 50 to 90% ethanol aqueous solution, preferably 75% ethanol aqueous solution.
In one embodiment of the present invention, in step 14), the diacetyl diphenylmethane or diacetyl dimethylbenzene methane has the following chemical structure:
Figure BDA0003316305780000051
wherein R is1、R2、R3Free selection of CH3Or H, preferably, R1、R2And R3The method comprises the following steps:
1)R1＝R2＝-CH3，R3h; or 2) R1＝H，R2＝R3＝-CH3(ii) a Or 3) R1＝-CH3，R2＝R3H; or 4) R1＝R2＝H，R3＝-CH3；
In one embodiment of the present invention, in step 21), the molar ratio of bromoethane to magnesium powder is 1.0: 1.0-1.2, preferably 1.0:1.1
In one embodiment of the present invention, in step 21), the reaction conditions are: after the dropwise addition, the temperature is raised to 40 ℃ for reaction for 1 h.
In one embodiment of the present invention, in step 22), the obtained ethyl grignard reagent is cooled to below 20 ℃, and a mixed solution of alkyne monomer p-diacetylene diphenylmethane or p-diacetylene diphenylmethane with a side methyl group and tetrahydrofuran is added dropwise, wherein the concentration of the alkyne monomer p-diacetylene diphenylmethane or p-diacetylene diphenylmethane with a side methyl group is 1.0 to 1.5mol/L, preferably 1.2 mol/L.
In one embodiment of the present invention, in step 22), the reaction conditions are: after the acetylene monomer is added, reflux reaction is carried out for 1.5h at 70 ℃.
In one embodiment of the present invention, in step 23), dichlorosilane is added in a molar ratio of the alkyne monomer p-diacetylene diphenylmethane or p-diacetylene diphenylmethane with a pendant methyl group to dichlorosilane of from 1:0.5 to 0.75, preferably 1: 0.67.
In one embodiment of the present invention, in step 23), the dichlorosilane is dimethyldichlorosilane or methylphenyldichlorosilane.
In one embodiment of the present invention, in step 23), the polymerization conditions are: after the dropwise addition, the reaction is carried out for 3 hours at 70 ℃.
In one embodiment of the present invention, in step 24), the extraction solvent is selected from one of toluene or dichloromethane, preferably dichloromethane.
In one embodiment of the invention, in step 24), the resin is obtained by washing with deionized water to be nearly neutral, drying, filtering, distilling under reduced pressure to remove the solvent, and drying in a vacuum oven at 60 ℃ for 4 hours.
In one embodiment of the present invention, in step 24), the resin is a silicon aryne resin having a p-diacetylene diphenylmethane structure.
In one embodiment of the invention, a method for synthesizing silicon aryne resin with a p-diacetyl diphenylmethane structure comprises the following steps:
1) synthesis of diacetyl diphenyl methane or diacetyl dimethyl phenyl methane
11) Dropwise adding sodium nitrite aqueous solution into diaminodi (methyl) phenylmethane at the temperature of 0 ℃ and the concentration of hydrochloric acid or sulfuric acid of 30% to prepare a diazonium salt solution; and dropwise adding the mixture into a KI solution at room temperature, reacting at room temperature for 24 hours, extracting with dichloromethane, washing with anhydrous sodium sulfite and anhydrous sodium carbonate respectively, drying to remove the solvent, and recrystallizing with ethanol to obtain diiodo-di (methyl) phenylmethane. Wherein the molar ratio of sodium nitrite to diaminodi (methyl) phenylmethane is 2.2: 1.0. The molar ratio of potassium iodide to diaminodi (methyl) phenylmethane was 2.5: 1.0.
12) Under the catalysis of 1% of bis (triphenylphosphine) palladium dichloride and 1% of cuprous iodide, carrying out Sonogashira reaction on diiodo di (methyl) phenylmethane and trimethylethynyl silane at 30-70 ℃ (preferably 40 ℃), preserving heat for 16 hours, and washing with ethanol or acetonitrile to obtain a product, thus obtaining di (trimethylsilylethynyl) di (methyl) phenylmethane. Wherein the molar ratio of diiodo di (methyl) phenylmethane to trimethylethynyl silane is 1.0: 2.5.
13) Adding the product into a mixed solvent of methanol and tetrahydrofuran of potassium carbonate, removing trimethylsilane at the temperature of 30-65 ℃, and recrystallizing by using 75% ethanol aqueous solution to obtain diacetylene di (methyl) phenylmethane:
Figure BDA0003316305780000061
wherein: 1) r1＝R2＝-CH3，R3H; or 2) R1＝H，R2＝R3＝-CH3(ii) a Or 3) R1＝-CH3，R2＝R3H; or4)R1＝R2＝H，R3＝-CH3；
2) Synthesis of resins
21) Adding magnesium powder and tetrahydrofuran into a reaction bottle under the nitrogen atmosphere, reducing the temperature to be below 20 ℃, and dripping bromoethane into the reaction bottle to prepare an ethyl Grignard reagent;
22) dripping the alkyne monomer synthesized in the step 1) into the ethyl Grignard reagent obtained in the step (21) at the temperature of below 30 ℃ for reaction to prepare an alkynyl Grignard reagent;
23) dripping dichlorosilane into the alkynyl Grignard reagent obtained in the step (22) at the temperature of below 30 ℃, and polymerizing to obtain resin; wherein the molar ratio of alkyne to silane is 1: 0.5-0.75, preferably 1: 0.67.
24) Adding acetic acid and hydrochloric acid into the polymerization product to stop the reaction, adding toluene or dichloromethane to extract the polymer, washing the extract with water to neutrality, drying, and removing the solvent to obtain the resin.
The invention also provides a silicon-containing aryne resin composite material, and the silicon-containing aryne resin with the structure of p-diacetylene diphenylmethane is adopted as a raw material.
The invention also provides a preparation method of the silicon-containing aryne resin composite material, which comprises the following steps:
1) preparing a solution from silicon aryne resin with a p-diacetylene diphenylmethane structure, impregnating the resin solution with carbon fiber cloth, and drying to obtain a prepreg;
2) and removing the solvent from the obtained prepreg, and molding and solidifying the prepreg on a flat vulcanizing machine to obtain the composite material.
In one embodiment of the present invention, in step 1), the concentration of the solution prepared from the silicon aryne resin having a p-diacetylene diphenylmethane structure is 30 to 50%, preferably 35 to 40%.
In one embodiment of the present invention, in step 1), the solvent for preparing the solution of the silicon aryne resin with the structure of p-diacetylene diphenylmethane is one or more selected from tetrahydrofuran, methyltetrahydrofuran, toluene or dichloromethane, preferably tetrahydrofuran.
In one embodiment of the invention, in step 1), the carbon fibers used in the carbon fiber cloth are selected from T300 carbon fibers, T700 carbon fibers or T800 carbon fibers.
In one embodiment of the invention, in the step 2), the temperature of the mold pressing, curing and forming is 170-300 ℃, the time of curing and forming is 8-12 hours, and the pressure of forming is 0.5-3.0 MPa. The operation optimization conditions of the mould pressing solidification forming are as follows: keeping the temperature at 170 ℃ for 2h, 210 ℃ for 2h and 250 ℃ for 4h under the pressure of 3.0 MPa.
The invention introduces a nonpolar p-diacetylene diphenylmethane structure into a main chain to obtain the silicon-containing aryne resin with high heat resistance, has excellent dielectric property, improves the processing property of the resin by introducing the side group, and enables the resin which is difficult to form originally to be made into a casting body and a composite material, thereby realizing the availability of the resin.
Researches show that the resin prepared by the invention has better comprehensive performance, the processing window can reach 110 ℃, the bending strength of a resin casting body can reach 42.1MPa, the thermal decomposition temperature under nitrogen can reach 522 ℃, and the dielectric constant is 1-107Less than 3.0 in the Hz range; the T300 reinforced composite material has good mechanical property, the normal-temperature bending strength can reach 381.9MPa, and the interlaminar shear strength can reach 23.2 MPa. Is expected to be used as matrix resin of high-performance composite materials and is applied in the high-tech fields of aerospace and the like.
Compared with the prior art, the invention has the positive improvement effects that:
the invention synthesizes a series of diyne monomers of diphenylmethane (with side methyl) and silicon-containing aryne resin, and the introduction of the side group can greatly improve the processing performance of the silicon-containing aryne resin. The resin also has better comprehensive performance.
The silicon-containing side methyl aryne resin is a light yellow or light red solid, is stable and easy to store at normal temperature, has a wider processing window and reaches up to 110 ℃. The material can be polymerized, crosslinked and cured at 170-250 ℃, and has excellent mechanical property and thermal stability after curing, the bending strength of the material reaches 42.1MPa, and the decomposition temperature of the material in nitrogen is as high as 522 ℃.
The silicon-containing side methyl aryne resin composite material has excellent heat resistance and mechanical property, high bending strength, bending modulus and shearing strength, and bending strength reaching 381.9MPa, and is expected to be applied to the high-tech fields of aerospace and the like.
Detailed Description
The invention firstly provides a kind of silicon aryne resin with a structure of p-diacetylene diphenylmethane, which has the following structural formula:
Figure BDA0003316305780000081
wherein R is1、R2、R3Free selection of CH3Or H, R is methyl or phenyl, n is an integer of 1-5, preferably n is 2 or 3. Preferably, R1、R2And R3The method comprises the following steps:
1)R1＝R2＝R3h; or the like, or, alternatively,
2)R1＝R2＝-CH3，R3h; or the like, or, alternatively,
3)R1＝H，R2＝R3＝-CH3(ii) a Or the like, or, alternatively,
4)R1＝-CH3，R2＝R3h; or the like, or, alternatively,
5)R1＝R2＝H，R3＝-CH3。
the invention also provides a synthetic method of the silicon aryne resin with the structure of the p-diacetylene diphenylmethane, which comprises the following steps:
1) synthesis of p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with pendant methyl group
11) Dropwise adding sodium nitrite aqueous solution into diaminodiphenylmethane or homologues thereof under an acidic condition to prepare a diazonium salt solution;
12) dripping the diazonium salt solution into potassium iodide (KI) solution, extracting with a solvent after reaction, washing again, drying to remove the solvent, and recrystallizing to obtain p-diiododiphenylmethane or p-diiododiphenylmethane with lateral methyl;
13) adding triethylamine, tetrahydrofuran, trimethylethynylene silane, cuprous iodide and a palladium catalyst into diiododiphenylmethane or diiododiphenylmethane with lateral methyl, carrying out Sonogashira reaction in a nitrogen environment, and washing to obtain a product after the reaction to obtain p-bis (trimethylsilylethynyl) diphenylmethane or p-bis (trimethylsilylethynyl) diphenylmethane with lateral methyl;
14) adding p-bis (trimethylsilylethynyl) diphenylmethane or p-bis (trimethylsilylethynyl) diphenylmethane with a side methyl group into a mixed solvent of methanol and tetrahydrofuran, adding alkali, reacting, removing trimethylsilane, and recrystallizing to obtain p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with a side methyl group;
2) synthesis of resins
21) Under the atmosphere of nitrogen, dropwise adding ethyl bromide into a mixture of magnesium powder and tetrahydrofuran, and reacting to prepare an ethyl Grignard reagent;
22) reacting p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with side methyl in an ethyl Grignard reagent to prepare an alkynyl Grignard reagent;
23) cooling the obtained alkynyl Grignard reagent to below 20 ℃, dropwise adding dichlorosilane, and carrying out polymerization reaction to obtain a polymerization product;
24) adding a solvent into the polymerization product obtained in the step 23) for extraction, after the reaction liquid is cooled to below room temperature, sequentially dropwise adding glacial acetic acid and hydrochloric acid solution to stop the reaction, removing unreacted magnesium powder, washing the extracting solution with water to be neutral, drying, and removing the solvent to obtain the resin.
In some preferred embodiments of the invention, in step 11), the chemical formula of the diaminodiphenylmethane or a homologue thereof is as follows:
Figure BDA0003316305780000101
wherein R is1、R2、R3Free selection of CH3Or H.
In step 11), the acidic environment is obtained by one or more of nitric acid, hydrochloric acid, sulfuric acid or acetic acid, preferably hydrochloric acid or sulfuric acid. The concentration of the acid is 10-50%, preferably 30%. In step 11), the concentration of the sodium nitrite solution is 20% -35%, preferably 30%. In step 11), the dropping time of the sodium nitrite solution is10 min to 60min, preferably 15 min. In step 11), the temperature of the dropwise addition of the sodium nitrite solution is controlled to be from-20 ℃ to 10 ℃, preferably 0 ℃. In step 11), the molar ratio of sodium nitrite to diaminodiphenylmethane or a homologue thereof is 2.2: 1.0.
In some preferred embodiments of the present invention, in step 12), the diazonium salt solution is dropped into the potassium iodide solution under the reaction conditions: reacting at room temperature for 24h or more. In step 12), the selected solvent is one of toluene, ethyl acetate or dichloromethane, preferably dichloromethane. In step 12), washing with an aqueous sodium sulfite solution and an aqueous sodium carbonate solution, respectively. In the step 12), the solvent selected for recrystallization is 75-99% ethanol aqueous solution, preferably 95% ethanol aqueous solution. In step 12), the molar ratio of potassium iodide to diaminodiphenylmethane or a homologue thereof is 2.5: 1.0.
In some preferred embodiments of the present invention, in step 13), the selected palladium catalyst is one or more of bis-triphenylphosphine palladium dichloride or tetratriphenylphosphine palladium, preferably bis-triphenylphosphine palladium dichloride. In the step 13), copper iodide and palladium iodide catalysts are used as catalysts, and the molar equivalents of the copper iodide and palladium iodide catalysts are all 1%. In step 13), the conditions for performing the Sonogashira reaction are: after the reaction is carried out for 16 hours at 30-70 ℃, the reaction temperature is preferably 40 ℃. In step 13), after the Sonogashira reaction, filtering to obtain a filtrate, removing the solvent from the filtrate, and then washing. In step 13), washing with ethanol or acetonitrile to white or light yellow to obtain the product. In the step 13), the molar ratio of p-diiododiphenylmethane or p-diiododiphenylmethane having a pendant methyl group to trimethylethynylsilane is 1.0: 2.5.
In some preferred embodiments of the present invention, the volume ratio of methanol to tetrahydrofuran in step 14) is 1:2 to 2:1, preferably 1: 1. In the step 14), the alkali is one or more of sodium hydroxide, potassium hydroxide and potassium carbonate, preferably potassium carbonate. In the step 14), the removal of trimethylsilane is carried out at 30-65 ℃. In step 14), the solvent is removed, then petroleum ether is used for thermal extraction, and p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with side methyl is obtained after recrystallization. In the step 14), a solvent used for recrystallization is 50-90% ethanol water solution, preferably 75% ethanol water solution. In step 14), the diacetylene diphenylmethane or diacetylene dimethylbenzene methane has the following chemical structural formula:
Figure BDA0003316305780000111
wherein R is1、R2、R3Free selection of CH3Or H, preferably, R1、R2And R3The method comprises the following steps:
1)R1＝R2＝-CH3，R3h; or 2) R1＝H，R2＝R3＝-CH3(ii) a Or 3) R1＝-CH3，R2＝R3H; or 4) R1＝R2＝H，R3＝-CH3；
In some preferred embodiments of the present invention, in step 21), the molar ratio of bromoethane to magnesium powder is 1.0: 1.0-1.2, preferably 1.0: 1.1. In the step 21), the reaction conditions are as follows: after the dropwise addition, the temperature is raised to 40 ℃ for reaction for 1 h.
In some preferred embodiments of the present invention, in step 22), the obtained ethyl grignard reagent is cooled to below 20 ℃, and a mixed solution of alkyne monomer p-diacetylene diphenylmethane or p-diacetylene diphenylmethane with a pendant methyl group and tetrahydrofuran is added dropwise, wherein the concentration of alkyne monomer p-diacetylene diphenylmethane or p-diacetylene diphenylmethane with a pendant methyl group is 1.0 to 1.5mol/L, preferably 1.2 mol/L. In the step 22), the reaction conditions are as follows: after the acetylene monomer is added, reflux reaction is carried out for 1.5h at 70 ℃.
In some preferred embodiments of the invention, dichlorosilane is added in step 23) in a molar ratio of alkyne monomer to diacetyl diphenylmethane or p-diacetyl diphenylmethane with a pendant methyl group to dichlorosilane of from 1:0.5 to 0.75, preferably 1: 0.67. In the step 23), the dichlorosilane is dimethyldichlorosilane or methylphenyldichlorosilane. In step 23), the polymerization conditions are as follows: after the dropwise addition, the reaction is carried out for 3 hours at 70 ℃.
In some preferred embodiments of the present invention, in step 24), the extraction solvent is selected from one of toluene or dichloromethane, preferably dichloromethane. And 24), washing with deionized water until the solution is nearly neutral, drying, filtering, distilling under reduced pressure to remove the solvent, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain the resin. In the step 24), the resin is the silicon aryne resin with a p-diacetylene diphenylmethane structure.
The invention also provides a silicon-containing aryne resin composite material, and the silicon-containing aryne resin with the structure of p-diacetylene diphenylmethane is adopted as a raw material.
The invention also provides a preparation method of the silicon-containing aryne resin composite material, which comprises the following steps:
1) preparing a solution from silicon aryne resin with a p-diacetylene diphenylmethane structure, impregnating the resin solution with carbon fiber cloth, and drying to obtain a prepreg;
2) and removing the solvent from the obtained prepreg, and molding and solidifying the prepreg on a flat vulcanizing machine to obtain the composite material.
In some preferred embodiments of the present invention, in step 1), the concentration of the solution of the silicon aryne resin having a p-diacetylene diphenylmethane structure is 30 to 50%, preferably 35 to 40%. In the step 1), the solvent for preparing the solution from the silicon aryne resin with the structure of the p-diacetyl diphenylmethane is one or more of tetrahydrofuran, methyl tetrahydrofuran, toluene or dichloromethane, preferably tetrahydrofuran. In the step 1), the carbon fiber adopted by the carbon fiber cloth is T300 carbon fiber, T700 carbon fiber or T800 carbon fiber.
In some preferred embodiments of the invention, in the step 2), the temperature of the mold pressing, curing and forming is 170-300 ℃, the time of curing and forming is 8-12 hours, and the pressure of forming is 0.5-3.0 MPa. The operation optimization conditions of the mould pressing solidification forming are as follows: keeping the temperature at 170 ℃ for 2h, 210 ℃ for 2h and 250 ℃ for 4h under the pressure of 3.0 MPa.
The analytical test method used in the present invention is as follows:
the structural hydrogen nuclear magnetic resonance spectrum of the synthesized silicon-containing aryne resin of the invention (1H-NMR), infrared spectroscopy (FTIR) and Gel Permeation Chromatography (GPC); hydrogen nuclear magnetic resonance spectroscopy (1H-NMR) Using a model AVANCE III 400 Bruker model 89400 high resolution Fourier transform nuclear magnetic resonance spectrometer, operating frequency 400MHz, solvent CDCl3TMS is used as an internal standard; fourier Infrared Spectroscopy (FT-IR) analysis Using Nicolet iS10 Fourier Infrared Spectroscopy, KBr pellet method, from Nicolet, USA, scanning Range 4000--1Resolution of 0.09cm-1And the number of scanning times is 32. Gel Permeation Chromatography (GPC) analytical testing gel permeation chromatography, model Waters 1515, from Waters corporation, usa, was used, with polystyrene as an internal standard. Tetrahydrofuran was used as the extract at a flow rate of 1 mL/min.
The heat resistance of the cured resin was analyzed by Thermal Gravimetric Analysis (TGA) using a TGA/DSC 1LF model thermal gravimetric analyzer manufactured by METTLER TOLEDO, Switzerland, the temperature rise rate was 10 ℃/min, the temperature range was 50-900 ℃, and the flow rate of nitrogen gas was 60 mL/min.
The dielectric properties of the cured resin were measured by a wide-band dielectric spectrometer (NoVOCONTROL, Germany) using a Concept 40 wide-band dielectric spectrometer. Test frequency 10-1～107Hz。
The bending properties of the resin-cast body and the composite material were measured by a three-point bending method. Mechanical properties of the resin and the composite material are measured by using a Shenzhen New Miss material testing Limited SANS CMT 4204 type microcomputer-controlled electronic universal tester, 5-10 test sample bars are arranged in each group, and an average value is obtained for performance results. The bending strength and the bending modulus of the resin and fiber cloth reinforced resin composite material flat plate are tested according to GB/T1499-2005, the test loading speed is 2mm/min, and the test sample is continuously loaded to be damaged during the test. And (3) testing the interlaminar shear strength of the fiber cloth reinforced resin composite material flat plate according to JC/T773-1982, wherein the test loading speed is 2mm/min, and the test sample is continuously loaded to be damaged during the test.
The present invention will be described in detail with reference to specific examples.
Example 1
Preparation of poly (dimethylsilane-3, 3 '-dimethyl-4, 4' -diacetyl diphenylmethane) resin and composite material thereof
1) Synthesis of 3,3 '-dimethyl-4, 4' -diacetyl diphenylmethane
A2L three-neck flask is provided with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, 0.16mol of 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, 400ml of concentrated hydrochloric acid and 350ml of water are added into the flask, the flask is stirred, heated to 40 ℃ by a hot water bath to completely dissolve the 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, and then cooled to separate out, the system is in a milky suspension state at the moment, and the temperature is reduced to 0-5 ℃. Weighing 0.4mol of NaNO2Dissolving the mixture in 50ml of water, dripping the mixture into a flask, controlling the dripping speed to ensure that the mixture is dripped off within about 15 minutes, and reacting for 0.5 hour after the dripping is finished, wherein the temperature is controlled to be 0 ℃ in the process. And then 0.4mol of urea is taken and dissolved in 50ml of water, the mixture is dripped into a flask and reacts for 10min after the dripping is finished, and a yellow to orange diazonium salt solution is obtained for standby. In another 2L three-necked flask equipped with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, 150ml of water, 0.48mol of KI and 300ml of methylene chloride were placed, and then a diazonium salt solution was added dropwise thereto, and the reaction was terminated at room temperature for 24 hours while keeping stirring after the completion of the addition. At this time, the system is dark red, and is kept stand for layering, the upper layer is a water phase, and the lower layer is an organic phase. The mixture was separated with a separatory funnel, washed three times with a sodium sulfite solution and then three times with a sodium carbonate solution to obtain an orange solution, and anhydrous sodium sulfate was added thereto and dried overnight. The sodium sulfate is removed by suction filtration, the solvent is removed by reduced pressure distillation, and the 3,3 '-dimethyl-4, 4' -diiododiphenylmethane is obtained after recrystallization by ethanol, with the yield of 52.1 percent.
0.2mol of 3,3 '-dimethyl-4, 4' -diiodo diphenyl methaneAlkane was added to a 1L four-necked flask, and 500ml Et was added simultaneously3N, 200ml tetrahydrofuran, 0.002mol CuI and 0.002mol bis (triphenylphosphine) palladium dichloride, keeping the temperature at 30 ℃, starting stirring and slowly dripping 0.5mol of trimethylethynyl silane, slowly changing the system color into brown yellow with generation of solid triethylamine salt, after dripping, adjusting the temperature to 40 ℃, reacting for 16h, filtering to obtain filtrate, then distilling under reduced pressure to remove the solvent, washing with ethanol to obtain white crystalline 3,3 '-dimethyl-4, 4' -bis (trimethylsilylethynyl) diphenylmethane, and the yield is 72.3%.
Adding 0.25mol of potassium carbonate into a 500mL conical flask filled with 200mL of methanol and 200mL of diethyl ether, then adding 0.2mol of 3,3 '-dimethyl-4, 4' -bis (trimethylsilylethynyl) diphenylmethane into the flask, starting magnetic stirring, reacting at 30 ℃ for 24h to obtain yellow liquid, filtering, distilling under reduced pressure to remove the solvent to obtain a yellow solid crude product, and recrystallizing with 75% ethanol to obtain the 3,3 '-dimethyl-4, 4' -diacetylene diphenylmethane with the yield of 89.2%.
2) Preparation of poly (dimethylsilane-3, 3 '-dimethyl-4, 4' -diacetylene diphenylmethane) resin
Under the nitrogen atmosphere, 0.300mol of magnesium powder and 60mL of tetrahydrofuran are added into a 500mL four-neck flask provided with a stirrer, a constant pressure funnel, a thermometer and a condenser tube, a mixed solution of 0.240mol of bromoethane and 20mL of tetrahydrofuran is slowly dripped through the constant pressure funnel in an ice water bath for about 10min, and the mixture reacts at 40 ℃ for 1h after the dripping is finished, so that the gray ethyl Grignard reagent is prepared.
The reaction solution is cooled to below room temperature by adopting an ice water bath, then a mixed solution of 0.120mol of 3,3 '-dimethyl-4, 4' -diacetylene diphenylmethane and 100mL of tetrahydrofuran (the concentration of the alkyne monomer in the mixed solution is 1.2mol/L) is added, after 0.5h of dropwise addition, gas is discharged after the reaction, and the reflux reaction is continued for 1.5h at the temperature of 70 ℃.
The reaction solution is cooled to below room temperature, a mixed solution of 0.080mol of dimethyldichlorosilane and 20mL of tetrahydrofuran is added through a constant pressure funnel, the dropping time is about 10min, and after the dropping is finished, the reflux reaction is carried out for 3h at 70 ℃.
Evaporating most of the obtained product solutionAfter tetrahydrofuran, 200mL of toluene was added to the reaction system, the reaction mixture was cooled to room temperature or lower, a mixture of 0.240mol of glacial acetic acid and 20mL of toluene was added dropwise to terminate the reaction, and 50mL (25%) of hydrochloric acid solution was added dropwise to the flask. Transferring the reaction solution to a 1000mL separating funnel, washing the reaction solution with deionized water until the reaction solution is nearly neutral, separating an upper organic phase, and adding anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and drying in a vacuum oven at 60 ℃ for 4h to obtain the resin with the yield of 87.5%. Melting point 72 ℃.
Resin structure analysis:1H-NMR(CDCl3，ppm)：3.23(≡C-H)，0.47(Si-CH3)，2.40(Ar-CH3)，3.87(CH2) 6.89 to 7.38 (Ar-H); FT-IR (KBr pellet, cm)-1)：3282(C≡C-H)，2953(-CH3)，2151(-C≡C-)，1253(Si-CH3) (ii) a Gpc (thf): the number average molecular weight was 1864, the weight average molecular weight was 3268, and the polydispersity number was 1.75.
Pouring the poly (dimethylsilane-3, 3 '-dimethyl-4, 4' -diacetyl diphenylmethane) resin into a mould, and curing: curing at the temperature of 170 ℃/2 h +210 ℃/2 h +250 ℃/4 h to obtain the resin casting body. The flexural strength was 42.1MPa and the flexural modulus was 2.3 GPa. Under the nitrogen atmosphere, the weight loss 5% temperature is 493 ℃, and the residual rate at 800 ℃ is 61.2%. Has a dielectric constant of 10-1～107The frequency range of Hz is 2.92-3.02.
3) Preparation of composite materials
Dissolving resin in tetrahydrofuran solvent to obtain 35 wt% solution, and soaking the cut pieces with size of 15 × 10cm in the resin solution2The T300 carbon fiber of (1) is prepared by taking 12 layers of impregnated carbon fiber cloth and orderly overlapping, and removing the organic solvent in a vacuum oven; and placing the prepreg on a flat vulcanizing machine, and sequentially carrying out curing procedures of 170 ℃/curing for 2h +210 ℃/curing for 2h +250 ℃/curing for 4h under the pressure of 3MPa to prepare the silicon-containing aryne resin composite plate. The normal-temperature bending strength of the T300 reinforced composite material is 381.9MPa, the bending modulus is 52.2GPa, and the interlaminar shear strength is 23.2 MPa; the bending strength at 400 ℃ is 227.5MPa, the bending modulus is 38.0GPa, and the interlaminar shearThe strength was 13.3 MPa.
Example 2
Preparation of poly (dimethylsilane-2, 2 '-dimethyl-4, 4' -diacetyl diphenylmethane) resin and composite material thereof
1) Synthesis of 2,2 '-dimethyl-4, 4' -diacetyl diphenylmethane
The synthesis procedure of 2,2 '-dimethyl-4, 4' -diacetyl diphenylmethane is the same as that for 3,3 '-dimethyl-4, 4' -diacetyl diphenylmethane. 2,2 '-dimethyl-4, 4' -diiododiphenylmethane is synthesized by diazotization reaction of 2,2 '-dimethyl-4, 4' -diaminodiphenylmethane as raw material; 2,2 '-dimethyl-4, 4' -di (trimethylsilylethynyl) diphenylmethane is synthesized by Sonogashira reaction, and then trimethylsilane is removed to obtain the 2,2 '-dimethyl-4, 4' -diacetylene diphenylmethane.
2) Preparation of poly (dimethylsilane-2, 2 '-dimethyl-4, 4' -diacetylene diphenylmethane) resin
The synthesis of poly (dimethylsilane-2, 2 '-dimethyl-4, 4' -diacetylene diphenylmethane) resin was the same as the resin in example 1, i.e. 2,2 '-dimethyl-4, 4' -diacetylene diphenylmethane was used as an alkyne monomer, and the poly (dimethylsilane-2, 2 '-dimethyl-4, 4' -diacetylene diphenylmethane) resin was synthesized by the preparation of an ethyl grignard reagent and the preparation of an alkyne grignard reagent, and then by the reaction with dimethyldichlorosilane.
The synthetic yield of the poly (dimethylsilane-2, 2 '-dimethyl-4, 4' -diacetyl diphenylmethane) resin is 90 percent, and the melting point is 70 ℃.
Resin structure analysis:1H-NMR(CDCl3，ppm)：2.95(≡C-H)，0.39(Si-CH3)，2.12(Ar-CH3)，3.80(CH2) 6.70 to 7.28 (Ar-H); FT-IR (KBr pellet, cm)-1)：3286(C≡C-H)，2965(-CH3)，2153(-C≡C-)，1250(Si-CH3) (ii) a Gpc (thf): the number average molecular weight was 1261, the weight average molecular weight was 1956, and the polydispersity number was 1.55.
The bending strength of the poly (dimethylsilane-2, 2 '-dimethyl-4, 4' -diacetyl diphenylmethane) resin casting was 33.1MPa, and the bending modulus was 2.8 GPa. Under nitrogen atmosphereThe weight loss 5% temperature is 519 ℃, and the residual rate at 800 ℃ is 81.6%. Has a dielectric constant of 10-1～107The range of Hz frequency is 2.90-2.97. The normal temperature bending strength of the T300 reinforced composite material is 364.6MPa, the bending modulus is 49.9GPa, and the interlaminar shear strength is 22.1 MPa; the bending strength at 400 ℃ is 165.1MPa, the bending modulus is 28.5GPa, and the interlaminar shear strength is 13.2 MPa.
Example 3
Preparation of poly (methylphenylsilane-4, 4' -diacetylene diphenylmethane) resin
1) Synthesis of 4, 4' -diacetyl diphenylmethane
Synthetic procedure references for 4, 4' -diacetyldiphenylmethane [ He J, et al, the Journal of Physical Chemistry C,2009,113, 6761-6767; Wai-Yeung W, et al, journal of organic and organic Polymers and Materials,18,155-162 ]. 4,4 '-diamino diphenylmethane is used as a raw material to synthesize 4, 4' -diiododiphenylmethane through diazotization reaction, 4 '-bis (trimethylsilylethynyl) diphenylmethane is synthesized through Sonogashira reaction, and trimethylsilane is removed to obtain 4, 4' -diacetylene diphenylmethane.
2) Preparation of poly (methylphenylsilane-4, 4' -diacetylene diphenylmethane) resin
The synthesis of poly (methylphenylsilane-4, 4 ' -diacetylene diphenylmethane) resin was the same as the synthesis of the resin in example 1, i.e. 4,4 ' -diacetylene diphenylmethane was used as an alkyne monomer, and the poly (methylphenylsilane-4, 4 ' -diacetylene diphenylmethane) resin was synthesized by the preparation of an ethyl grignard reagent and an alkyne grignard reagent, and then by the reaction with methylphenyldichlorosilane.
The synthetic yield of the poly (methyl phenyl silane 4, 4' -diacetyl diphenyl methane) resin is 87.5 percent. Melting point 72 ℃.
Resin structure analysis:1H-NMR(CDCl3，ppm)：3.03(≡C-H)，0.68ppm(Si-CH3)，3.95(CH2) 7.08 to 7.83 (Ar-H); FT-IR (KBr pellet, cm)-1)：3287(C≡C-H)，2963(-CH3)，2152(-C≡C-)，1251(Si-CH3)。
The bending strength of the poly (methylphenylsilane-4, 4' -diacetyldiphenylmethane) resin casting was 31.7MPa, and the bending modulus was 2.5 GPa. Under the nitrogen atmosphere, the weight loss 5% temperature is 455 ℃, and the residual rate at 800 ℃ is 77.4%.
Example 4
Preparation of poly (dimethylsilane-2, 2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin
1) Synthesis of 2,2 ', 3,3 ' -tetramethyl-4-4 ' -diacetyl diphenyl methane
The synthesis steps of 2,2 ', 3,3 ' -tetramethyl-4-4 ' -diacetyl diphenylmethane are the same as the synthesis steps of 3,3 ' -dimethyl-4, 4 ' -diacetyl diphenylmethane, 2 ', 3,3 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane is used as a raw material to synthesize 2,2 ', 3,3 ' -tetramethyl-4, 4 ' -diiododiphenylmethane through diazotization, 2 ', 3,3 ' -tetramethyl-4, 4 ' -bis (trimethylsilylethynyl) diphenylmethane is synthesized through Sonogashira reaction, and trimethylsilane is removed to obtain 2,2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetyl diphenylmethane. Wherein the reaction temperature in the step of removing trimethyl silicon is 50 ℃, and tetrahydrofuran/methanol is used for recrystallization in the purification of 2,2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane.
2) Preparation of poly (dimethylsilane-2, 2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin
The synthesis of poly (dimethylsilane-2, 2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin was the same as the synthesis of the resin of example 1, i.e. 2,2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane was used as an alkyne monomer, and the poly (dimethylsilane-2, 2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin was synthesized by the preparation of an ethyl grignard reagent, the preparation of an alkyne grignard reagent, and the reaction with dimethyldichlorosilane.
The synthetic yield of the poly (dimethylsilane-2, 2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetyl diphenyl methane) resin is 85 percent, and the melting point is 195 ℃.
Resin structure analysis:1H-NMR(CDCl3，ppm)：3.23(≡C-H)，0.48(Si-CH3) 2.13 and 2.47 (Ar-CH)3)，3.93(CH2) 6.62 to 7.23 (Ar-H); FT-IR (KBr pellet)，cm-1)：3300(C≡C-H)，2961(-CH3)，2148(-C≡C-)，1251(Si-CH3) (ii) a Gpc (thf): the number average molecular weight was 902, the weight average molecular weight was 1375, and the polydispersity number was 1.52.
The poly (dimethylsilane-2, 2 ', 3,3 ' -tetramethyl-4, 4 ' -diacetyl diphenyl methane) resin condensate has 5 percent weight loss at 467 ℃ and 63.8 percent residual rate at 800 ℃ in nitrogen atmosphere.
Example 5
Preparation of poly (dimethylsilane-2, 2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin
1) Synthesis of 2,2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetyl diphenyl methane
The synthesis of 2,2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetyl diphenylmethane is the same as the synthesis of 3,3 ' -dimethyl-4, 4 ' -diacetyl diphenylmethane, 2 ', 5,5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane is used as a raw material to synthesize 2,2 ', 5,5 ' -tetramethyl-4, 4 ' -diiododiphenylmethane through diazotization, 2 ', 5,5 ' -tetramethyl-4, 4 ' -bis (trimethylsilylethynyl) diphenylmethane is synthesized through Sonogashira reaction, and 2,2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetyl diphenylmethane is obtained by removing trimethylsilane. Wherein the reaction temperature in the step of removing trimethyl silicon is 50 ℃, and tetrahydrofuran/methanol is used for recrystallization in the purification of 2,2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane.
2) Preparation of poly (dimethylsilane-2, 2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin
Synthesis of poly (dimethylsilane-2, 2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin the same procedure as that of the resin of example 1 was followed, i.e., 2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane was used as an alkyne monomer, and poly (dimethylsilane-2, 2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetylene diphenylmethane) resin was synthesized by the preparation of an ethyl Grignard reagent, the preparation of an alkyne Grignard reagent, and the reaction with dimethyldichlorosilane.
The synthetic yield of the poly (dimethylsilane-2, 2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetyl diphenyl methane) resin is 87%, and the melting point is 172 ℃.
Resin structure analysis:1H-NMR(CDCl3，ppm)：3.23(≡C-H)，0.48(Si-CH3) 2.15 and 2.34 (Ar-CH)3)，3.81(CH2) 6.67 to 7.30 (Ar-H); FT-IR (KBr pellet, cm)-1)，3287(C≡C-H)，2967(-CH3)，2153(-C≡C-)，1247(Si-CH3) (ii) a Gpc (thf): the number average molecular weight was 902, the weight average molecular weight was 1375, and the polydispersity number was 1.52.
The poly (dimethylsilane-2, 2 ', 5,5 ' -tetramethyl-4, 4 ' -diacetyl diphenyl methane) resin condensate has the weight loss of 5 percent at the temperature of 493 ℃ and the residual rate of 70.7 percent at the temperature of 800 ℃ under the nitrogen atmosphere.
Example 6
Preparation of poly (dimethylsilane-4, 4' -diacetylene diphenylmethane) resin
1) Synthesis of 4, 4' -diacetyl diphenylmethane
Synthetic procedure references for 4, 4' -diacetyldiphenylmethane [ He J, et al, the Journal of Physical Chemistry C,2009,113, 6761-6767; Wai-Yeung W, et al, journal of organic and organic Polymers and Materials,18,155-162 ]. 4,4 '-diamino diphenylmethane is used as a raw material to synthesize 4, 4' -diiododiphenylmethane through diazotization reaction, 4 '-bis (trimethylsilylethynyl) diphenylmethane is synthesized through Sonogashira reaction, and trimethylsilane is removed to obtain 4, 4' -diacetylene diphenylmethane.
2) Preparation of poly (dimethylsilane-4, 4' -diacetylene diphenylmethane) resin
The synthesis of poly (dimethylsilane-4, 4 ' -diacetylene diphenylmethane) resin was the same as the synthesis of the resin of example 1, i.e. 4,4 ' -diacetylene diphenylmethane was used as an alkyne monomer, and the poly (methylphenylsilane-4, 4 ' -diacetylene diphenylmethane) resin was synthesized by the preparation of an ethyl grignard reagent and an alkyne grignard reagent, and then by the reaction with dimethyldichlorosilane.
The synthetic yield of the poly (dimethylsilane-4, 4' -diacetyl diphenylmethane) resin is 83 percent.
Resin structure analysis:1H-NMR(CDCl3，ppm)：3.01(≡C-H)，0.43(Si-CH3)，3.94(CH2) 7.06 to 7.39 (Ar-H); FT-IR (KBr pellet, cm)-1)，3287(C≡C-H)，2962(-CH3)，2157(-C≡C-)，1250(Si-CH3)。
Under the nitrogen atmosphere, the poly (dimethylsilane-4, 4' -diacetyl diphenyl methane) resin condensate has the weight loss of 5 percent at 522 ℃ and the residual rate of 82.8 percent at 800 ℃.
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. A silicon aryne resin with a p-diacetylene diphenylmethane structure is characterized in that the structural formula is as follows:
Figure FDA0003316305770000011
wherein R is1、R2、R3Free selection of CH3Or H, R is methyl or phenyl, and n is an integer of 1-5.
2. The silicon aryne resin with the structure of p-diacetylene diphenylmethane according to claim 1, wherein R is1、R2And R3The method comprises the following steps:
1)R1＝R2＝R3h; or the like, or, alternatively,
2)R1＝R2＝-CH3，R3h; or the like, or, alternatively,
3)R1＝H，R2＝R3＝-CH3(ii) a Or the like, or, alternatively,
4)R1＝-CH3，R2＝R3h; or the like, or, alternatively,
5)R1＝R2＝H，R3＝-CH3。
3. the silicon aryne resin having a p-diacetylene diphenylmethane structure according to claim 1, wherein the number average molecular weight of the silicon aryne resin having a p-diacetylene diphenylmethane structure is 900 to 2500, and the polydispersity is 1.2 to 1.8.
4. A method for synthesizing a silicon aryne resin having a p-diacetylene diphenylmethane structure according to any one of claims 1 to 3, comprising the steps of:
1) synthesis of p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with pendant methyl group
11) Dropwise adding sodium nitrite aqueous solution into diaminodiphenylmethane or homologues thereof under an acidic condition to prepare a diazonium salt solution;
12) dripping a diazonium salt solution into a potassium iodide solution, extracting with a solvent after reaction, washing again, drying to remove the solvent, and recrystallizing to obtain p-diiododiphenylmethane or p-diiododiphenylmethane with a side methyl group;
13) adding triethylamine, tetrahydrofuran, trimethylethynylene silane, cuprous iodide and a palladium catalyst into diiododiphenylmethane or diiododiphenylmethane with lateral methyl, carrying out Sonogashira reaction in a nitrogen environment, and washing to obtain a product after the reaction to obtain p-bis (trimethylsilylethynyl) diphenylmethane or p-bis (trimethylsilylethynyl) diphenylmethane with lateral methyl;
14) adding p-bis (trimethylsilylethynyl) diphenylmethane or p-bis (trimethylsilylethynyl) diphenylmethane with a side methyl group into a mixed solvent of methanol and tetrahydrofuran, adding alkali, reacting, removing trimethylsilane, and recrystallizing to obtain p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with a side methyl group;
2) synthesis of resins
21) Under the atmosphere of nitrogen, dropwise adding ethyl bromide into a mixture of magnesium powder and tetrahydrofuran, and reacting to prepare an ethyl Grignard reagent;
22) reacting p-diacetyl diphenylmethane or p-diacetyl diphenylmethane with side methyl in an ethyl Grignard reagent to prepare an alkynyl Grignard reagent;
23) cooling the obtained alkynyl Grignard reagent to below 20 ℃, dropwise adding dichlorosilane, and carrying out polymerization reaction to obtain a polymerization product;
24) adding a solvent into the polymerization product obtained in the step 23) for extraction, after the reaction liquid is cooled to below room temperature, sequentially dropwise adding glacial acetic acid and hydrochloric acid solution to stop the reaction, removing unreacted magnesium powder, washing the extracting solution with water to be neutral, drying, and removing the solvent to obtain the resin.
5. The method for synthesizing a silicon aryne resin having a p-diethynyldiphenylmethane structure according to claim 4, wherein the silicon aryne resin having a p-diethynyldiphenylmethane structure,
in step 11), the chemical structural formula of the diaminodiphenylmethane or the homologue thereof is as follows:
Figure FDA0003316305770000021
wherein R is1、R2、R3Free selection of CH3Or H;
in the step 13), the selected palladium catalyst is one or more of bis (triphenylphosphine) palladium dichloride or tetrakis (triphenylphosphine) palladium;
in step 14), the diacetylene diphenylmethane or diacetylene dimethylbenzene methane has the following chemical structural formula:
Figure FDA0003316305770000022
wherein R is1、R2、R3Free selection of CH3Or H.
6. The method for synthesizing a silicon aryne resin with a p-diacetylene diphenylmethane structure according to claim 4, wherein in the step 23), dichlorosilane is added according to the molar ratio of the alkyne monomer to the diacetylene diphenylmethane or the p-diacetylene diphenylmethane with a side methyl group to the dichlorosilane being 1: 0.5-0.75;
in the step 23), the dichlorosilane is dimethyldichlorosilane or methylphenyldichlorosilane.
7. A silicon-containing aryne resin composite material is characterized in that the silicon-containing aryne resin with a p-diacetylene diphenylmethane structure disclosed by any one of claims 1 to 3 is adopted as a raw material.
8. The method for preparing the silicon-containing aryne resin composite material according to claim 7, comprising the steps of:
1) preparing a solution from silicon aryne resin with a p-diacetylene diphenylmethane structure, impregnating the resin solution with carbon fiber cloth, and drying to obtain a prepreg;
2) and removing the solvent from the obtained prepreg, and molding and solidifying the prepreg on a flat vulcanizing machine to obtain the composite material.
9. The preparation method of the silicon-containing aryne resin composite material according to claim 8, wherein in the step 1), the concentration of the silicon aryne resin with the structure of p-diacetylene diphenylmethane is 30-50% after the silicon aryne resin is prepared into a solution;
in the step 1), the carbon fiber adopted by the carbon fiber cloth is T300 carbon fiber, T700 carbon fiber or T800 carbon fiber.
10. The preparation method of the silicon-containing aryne resin composite material according to claim 8, wherein in the step 2), the temperature of the mould pressing, curing and forming is 170-300 ℃, the time of curing and forming is 8-12 h, and the pressure of the forming is 0.5-3.0 Mpa.
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