CN110423350B - Low-temperature cured high-heat-resistance silicon-based phenylalkyne resin and preparation method and application thereof - Google Patents
Low-temperature cured high-heat-resistance silicon-based phenylalkyne resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of resin, and particularly relates to a low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin and a preparation method thereof. The resin is prepared and obtained by taking 1,3, 5-triethynyl benzene, m-diethynyl benzene and methyl dichlorosilane as main raw materials and adopting a synthesis method of a Grignard reagent under the protection of inert gas, wherein the ethynyl is taken as a terminal group, and the silicon-based phenylalkyne resin has high heat resistance. The resin is easy to dissolve in common solvents such as toluene, tetrahydrofuran and the like; the viscosity is moderate at normal temperature and the melting point is low; the processing temperature is 20-155 ℃, and the processing performance is good; the curing temperature is lower than 115 ℃, the maximum 5% decomposition temperature of the resin condensate can reach 684.8 ℃, and the resin condensate is suitable for preparing high-performance composite material matrixes, high-temperature-resistant coatings and photoelectric materials and can be applied to the fields of space vehicles and photoelectric materials.
Description
Technical Field
The invention belongs to the technical field of resin, and particularly relates to a low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin as well as a preparation method and application thereof.
Background
The high-temperature resistant hybrid resin containing silicon element becomes a research hotspot due to the excellent heat resistance and dielectric property. The special composition and molecular structure of the silicon-introduced aryl polyacetylene resin enable the silicon-introduced aryl polyacetylene resin to integrate the organic matter characteristics and the inorganic matter functions, and the introduction of the silicon element enables the polymer to have excellent heat resistance, excellent dielectric properties and high-temperature ceramic properties. Can be used for preparing ceramic precursors, high-performance composite material matrixes, high-temperature ablation-resistant materials and the like, and has wide application prospects in the fields of space vehicles, photoelectric materials and the like. Itoh [1 ]]The dehydrogenation coupling reaction of the single substituted alkyne monomer and the hydrogen-containing silane under the catalytic condition of the MgO solid catalyst is researched to obtain the silicon-containing aryne resin. The resin has 5% decomposition temperature up to 860 ℃ under the condition of argon, the thermal decomposition residue rate at 1000 ℃ is over 90%, and the heat resistance is very excellent; the excellent high heat resistance is derived from a complex crosslinking network formed by a silicon-hydrogen addition reaction between a-Si-H bond and-C [ identical to ] CH, a cyclotrimerization reaction between Ph-C [ identical to ] CH and-CH [ identical to ] CH and a Diels-Alder reaction; its disadvantages are high curing temperature and narrow processing window. Yanhao [2]]Para-polyarylates using organosilanesModifying and researching the polyacetylene, and synthesizing the aryl polyacetylene resin with a novel structure by using halogenated silane and aryl acetylene as raw materials; the resin is liquid or solid with low melting point at normal temperature, and the cured resin has excellent heat resistance. Jianghuan [3]]Taking m-diethynylbenzene and bis (dimethylamino) dimethylsilane as raw materials, and synthesizing silicon-containing aryne resin by single-step silanization under the catalysis of zinc chloride; the resin product is in a flowing state at normal temperature, the processing temperature is 40-180 ℃, and the processing window is very wide; however, the cured resin is represented by the formula N 25% decomposition temperature (T) under atmosphered5) At 587 c, further studies are needed to enhance the heat resistance.
Disclosure of Invention
The invention aims to provide a low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin, a preparation method and application thereof, solves the problem of overhigh curing temperature of the resin, and synthesizes a novel high-heat-resistance silicon-based phenyl alkyne resin.
The technical scheme of the invention is as follows:
a low-temperature cured high-heat-resistance silylphenylalkyne resin has the following structure, wherein the former is a product structural formula obtained by reacting 1,3, 5-triethylynylbenzene with methyl dichlorosilane (example 1), and the latter is a product structural formula obtained by copolymerizing a mixture of m-diethynylbenzene and 1,3, 5-triethylynylbenzene with methyl dichlorosilane (examples 2-4).
Or alternatively
The invention also provides a preparation method of the low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin, which mainly comprises the following steps:
(1) under the protection of inert gas, reacting magnesium powder with bromoethane to generate an ethyl magnesium bromide Grignard reagent;
(2) reacting the reaction product with an alkynyl monomer to generate an ethynyl magnesium bromide Grignard reagent;
(3) and (3) reacting the reaction product with methyl dichlorosilane to obtain the silicon-based phenylalkyne resin with two ends being terminated by ethynyl.
According to the preparation method of the low-temperature cured high-heat-resistance silicon-based phenylalkyne resin, the molar ratio of the alkyne-containing monomer to the methyl dichlorosilane is 1:1, the molar ratio of the m-diethynylbenzene to the 1,3, 5-triethynylbenzene is 0:1,2:1,5:1 and 10:1 respectively, and the alkyne-containing monomer is m-diethynylbenzene and 1,3, 5-triethynylbenzene.
Furthermore, the molar ratio of bromoethane to alkynyl in the alkynyl-containing monomer is 1.1:1, the molar ratio of magnesium powder to alkynyl in the alkynyl-containing monomer is 1.0-1.3:1, and the optimal feeding ratio is 1.2: 1.
The alkyne-containing monomer used is m-diethynylbenzene and 1,3, 5-triethynylbenzene.
According to the preparation method of the low-temperature cured high-heat-resistance silicon-based phenylalkyne resin, the length of the molecular chain of the resin is adjusted by adjusting the input ratio of the alkyne-containing monomer to silane, and the density of functional groups capable of participating in curing reaction in the polymer and the content of silicon in the structure are controlled.
The values of m and n are controlled by the feeding proportion of m-diethynylbenzene and 1,3, 5-triethynylbenzene, namely the larger the proportion of m-diethynylbenzene is, the larger the value of m is.
Further, the solvents used for the synthesis of the alkyne grignard reagent are typically Tetrahydrofuran (THF), 2-methyltetrahydrofuran, toluene. 2-methyltetrahydrofuran is preferred because acetylenic monomers are well soluble in 2-methyltetrahydrofuran.
The invention also provides the low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin or the low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin prepared by the preparation method, and the application of the low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin in preparing high-performance composite material matrixes, high-temperature-resistant coatings and photoelectric materials.
The invention also provides the low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin or the low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin prepared by the preparation method, and the application of the low-temperature cured high-heat-resistance silicon-based phenyl alkyne resin in the fields of space vehicles and photoelectric materials.
The silane used in the study was methyldichlorosilane.
Before the reaction is started, the reagents used are dried, and water vapor in the device is removed and nitrogen is introduced for protection.
Synthesis of ethyl magnesium bromide grignard reagent: adding magnesium powder and 2-methyltetrahydrofuran into a four-neck flask, and slowly dropwise adding a mixed solution of bromoethane and 2-methyltetrahydrofuran. After the dropwise addition, the reaction was carried out at a constant temperature of 45 ℃ for 2 hours.
Synthesis of alkynyl magnesium bromide grignard reagent: slowly dripping a mixed solution containing alkynyl monomers and 2-methyltetrahydrofuran into the ethyl magnesium bromide Grignard reagent. After the dropwise addition, the reaction was carried out at a constant temperature of 82 ℃ for 2 hours.
Under the protection of nitrogen, methyl dichlorosilane is dripped into the product, and the mixture reacts for 1 hour at the constant temperature of 45 ℃ and for 2 hours at the constant temperature of 82 ℃. To generate the ethynyl terminated silicon-based phenylalkyne resin.
The synthetic resin has the following structure:
or
After the reaction is finished, glacial acetic acid and dilute hydrochloric acid are added, and the system gradually generates precipitate. Adding methyl tert-butyl ether, and stirring for 10 min. The turbid liquid is transferred to a separating funnel, a proper amount of deionized water is added, the precipitate disappears, and the system becomes an orange yellow transparent state. Shaking, standing for layering, and discharging the lower layer liquid. And (5) repeating the steps for washing for 4-5 times until the solution is neutral.
And adding anhydrous sodium sulfate into the product, drying for 12h, filtering, and distilling under reduced pressure to obtain the yellow brown viscous resin.
The formula and the synthesis steps for preparing the resin disclosed by the invention are as follows (in parts by weight): 6-8 parts of bromoethane, 1-2 parts of magnesium powder and 20-25 parts of 2-methyltetrahydrofuran, and reacting for 2 hours at 40-50 ℃ to synthesize an ethyl magnesium bromide Grignard reagent; then, dropwise adding 3-5 parts of m-diethynylbenzene, 1,3, 5-triethynylbenzene and 55-65 parts of 2-methyltetrahydrofuran mixed solution to synthesize an alkynyl magnesium bromide Grignard reagent at 82 ℃; and then dropwise adding 5-8 parts of methyl dichlorosilane and 10-15 parts of 2-methyltetrahydrofuran, reacting for 1h at 45 ℃, raising the temperature to 82 ℃ and reacting for 2h to finally prepare the silicon-based phenyl alkyne resin.
Compared with the existing modified silicon-containing aryne resin, the silicon-based aryne resin prepared by the invention has the following characteristics: the solubility is good, and the processability is good; low-temperature curing and short curing time; the cured resin has good heat resistance.
The resin is easy to dissolve in common solvents, and has moderate viscosity at normal temperature, low melting point and good processing performance. The curing temperature is lower than 115 ℃, the 5% decomposition temperature of the resin condensate can reach 684 ℃ at most, and the preparation method is suitable for preparing high-performance composite material matrixes, high-temperature-resistant coatings and photoelectric materials and can be applied to the fields of space vehicles and photoelectric materials.
Drawings
FIG. 1 NMR chart of the resin of example 1;
FIG. 2 Fourier transform Infrared Spectroscopy of the resin of example 1.
Detailed description of the preferred embodiments
The present invention is described in detail below with reference to specific examples, which are provided to assist those skilled in the art in further understanding the present invention, but are not intended to limit the present invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
1.73g of magnesium powder (0.072mol) and 10mL of 2-methyltetrahydrofuran were added to a four-necked flask, and 7.19g of bromoethane (0.066mol) and 10mL of 2-methyltetrahydrofuran were slowly added dropwise. After the dropwise addition, the reaction was carried out at a constant temperature of 45 ℃ for 2 hours. 3.0g of a mixed solution of 1,3, 5-triethylynylbenzene (0.02mol) and 50mL of 2-methyltetrahydrofuran was slowly added dropwise thereto, and the mixture was reacted at 82 ℃ for 2 hours. 2.30g of methyldichlorosilane (0.02mol) and 30mL of 2-methyltetrahydrofuran are added dropwise, the mixture reacts for 1h at the constant temperature of 45 ℃, and the temperature is raised to 82 ℃ for 2h at the constant temperature. Then, 2mL of glacial acetic acid and 2mL of diluted hydrochloric acid were added dropwise and stirred for 0.5 h. Then adding methyl tert-butyl ether as a solvent, adding deionized water, and washing for five to eight times. Drying with anhydrous sodium sulfate for 10h, filtering, and distilling under reduced pressure to obtain brown yellow resin with certain fluidity and moderate resin viscosity.1H-NMR results: -Si-CH3Chemical shifts are 0.4-0.5 ppm, chemical shifts of-C.ident.CH are 3.09ppm, and chemical shifts of-Si-H are 4.5 ppm; FT-IR results: 3296cm-1Belongs to-C ≡ CH stretching vibration peak, 2964cm-1Belongs to the-Si-CH 3 stretching vibration peak of 2165cm-1Extensional vibration peaks ascribed to-C ≡ C-and-Si-H. The resulting resin was soluble in toluene. The curing program is 115 ℃/1h, 130 ℃/1h, 150 ℃/2h, 170 ℃/2h, 200 ℃/2 h. After the resin is cured, a bright black dense block solid is obtained. The resin cured product had a 5% decomposition temperature of 560.2 ℃ and a residual rate of 90.2% at 800 ℃.
Example 2
4.032g of magnesium powder (0.168mol) and 10mL of 2-methyltetrahydrofuran were added to the four-necked flask, and 16.78g of bromoethane (0.154mol) and 10mL of 2-methyltetrahydrofuran were slowly added dropwise. After the dropwise addition, the reaction is carried out for 2 hours at a constant temperature of 45 ℃. A mixed solution of 5.04g of m-diethynylbenzene (0.04mol), 3.00g of 1,3, 5-triethynylbenzene (0.02mol) and 40mL of 2-methyltetrahydrofuran was slowly added dropwise thereto, and the mixture was reacted at 82 ℃ for 2 hours. 6.90g of methyldichlorosilane (0.06mol) and 30mL of 2-methyltetrahydrofuran are added dropwise, the mixture reacts for 1h at the constant temperature of 45 ℃, and the temperature is raised to 82 ℃ for 2h at the constant temperature. The other steps are the same as example 1, and a yellow brown resin is finally obtained, and the resin is in a medium viscosity state at room temperature.
1The H-NMR results and FT-IR results were the same as in example 1. The resulting resin was soluble in toluene. The curing procedure was: 115 ℃/1h, 130 ℃/1h, 150 ℃/2h, 170 ℃/2h, 200 ℃/2 h. After the resin is cured, a bright black dense block solid is obtained. The 5% decomposition temperature of the cured resin was 562.4 ℃ and the 800 ℃ residual ratio was 88.4%.
Example 3
7.488g of magnesium powder (0.312mol) and 10mL of 2-methyltetrahydrofuran were added to a four-necked flask, and 31.59g of bromoethane (0.286mol) and 10mL of 2-methyltetrahydrofuran were slowly added dropwise. After the dropwise addition, the reaction was carried out at a constant temperature of 45 ℃ for 2 hours. A mixed solution of 12.60g of m-diethynylbenzene (0.1mol), 3.00g of 1,3, 5-triethylynylbenzene (0.02mol) and 50mL of 2-methyltetrahydrofuran was slowly added dropwise thereto, and the mixture was reacted at 82 ℃ for 2 hours. 13.804g of methyl dichlorosilane (0.12mol) and 30mL of 2-methyl tetrahydrofuran are added dropwise, the mixture reacts for 1h at the constant temperature of 45 ℃, and the mixture is heated to 82 ℃ and reacts for 2h at the constant temperature. The other steps are the same as example 1, and finally the dark brown viscous resin is obtained.
1The H-NMR and FT-IR results were the same as in example 1. The resulting resin was soluble in toluene. The curing procedure was: 115 ℃/1h, 130 ℃/1h, 150 ℃/2h, 170 ℃/2h, 200 ℃/2 h. After the resin is cured, a bright black dense block solid is obtained. The 5% decomposition temperature of the cured product was 575.7 ℃ and the 800 ℃ residual ratio was 86.7%.
Example 4
13.248g of magnesium powder (0.552mol) and 10mL of 2-methyltetrahydrofuran were added to a four-necked flask, and 55.134g of bromoethane (0.506mol) and 10mL of 2-methyltetrahydrofuran were slowly added dropwise. After the dropwise addition, the reaction was carried out at a constant temperature of 45 ℃ for 2 hours. A mixed solution of 25.20g of m-diethynylbenzene (0.2mol), 3.00g of 1,3, 5-triethylynylbenzene (0.02mol) and 50mL of 2-methyltetrahydrofuran was slowly added dropwise thereto, and the mixture was reacted at 82 ℃ for 2 hours. 25.30g of methyldichlorosilane (0.22mol) and 30mL of 2-methyltetrahydrofuran are added dropwise, the mixture reacts for 1h at the constant temperature of 45 ℃, and the temperature is raised to 82 ℃ for 2h at the constant temperature. The other steps are the same as the example 1, and finally the brown yellow viscous state resin is obtained.
1The H-NMR and FT-IR results were the same as in example 1. The resulting resin was soluble in toluene. The curing procedure was: 115 ℃/1h, 130 ℃/1h, 150 ℃/2h, 170 ℃/2h, 200 ℃/2 h. . After the resin is cured, a bright black dense block solid is obtained. The 5% decomposition temperature of the cured product was 684.4 ℃ and the 800 ℃ residual ratio was 92.7%.
The above-mentioned embodiments are merely preferred embodiments of the present invention, and not intended to limit the scope of the invention, which is defined by the claims and the accompanying drawings.
[ reference documents ]
[1]Itoh M.Anovel synthesis of a highly heat-resistant organosilicon polymer using base catalysts[J].Catalysis Surveys from Japan.1999,3(1):61-69.
[2] The synthesis and performance of novel silicon-containing arylpolyacetylene resins [ J ]. petrochemical industry [ 2004,33(9):880-884 ].
[3] Jiangxing, Dengsheng, Ruan Xiangzhen, zinc chloride catalyzed synthesis of aryne resin containing silicon [ J ] high molecular material science and engineering 2017,33(11):18-21,28.
Claims (5)
1. A low-temperature cured high heat resistant silylphenylalkyne resin, characterized in that the high heat resistant resin has the following structure:
the low-temperature cured high-heat-resistance silicon-based benzyne resin is prepared by the following steps:
(1) under the protection of inert gas, generating an ethyl magnesium bromide Grignard reagent by the reaction of magnesium powder and bromoethane;
(2) reacting the reaction product with 1,3, 5-triethynyl benzene or m-diethynyl benzene and 1,3, 5-triethynyl benzene to generate ethynyl magnesium bromide;
(3) reacting the reaction product with chlorosilane to generate polyacetylene-based phenyl resin with two ends blocked by ethynyl;
the molar ratio of the alkyne-containing monomer to the methyldichlorosilane is 1: 0.5-1, and the molar ratio of the m-diacetylene benzene to the 1,3, 5-triacetylbenzene is 0:1,2:1,5:1,10: 1;
the mol ratio of bromoethane to alkynyl in the acetylene monomer is 1.1:1, and the mol ratio of magnesium powder to alkynyl in the acetylene monomer is 1.0-1.3: 1.
2. A method for preparing the low-temperature cured high heat-resistant silylphenylalkyne resin as claimed in claim 1, which comprises the following main steps:
(1) under the protection of inert gas, generating an ethyl magnesium bromide Grignard reagent by the reaction of magnesium powder and bromoethane;
(2) reacting the reaction product with 1,3, 5-triethynyl benzene or m-diethynyl benzene and 1,3, 5-triethynyl benzene to generate ethynyl magnesium bromide;
(3) and reacting the reaction product with chlorosilane to generate the polyacetylene-based phenyl resin with two ends capped by ethynyl.
3. The method for preparing a low-temperature cured high heat-resistant silylphenylalkyne resin according to claim 2, wherein the method comprises the following steps: the solvents used for synthesizing the alkyne Grignard reagent are tetrahydrofuran, 2-methyltetrahydrofuran and toluene.
4. The application of the low-temperature cured high-heat-resistant silicon-based phenylalkyne resin disclosed in claim 1 or the low-temperature cured high-heat-resistant silicon-based phenylalkyne resin prepared by the preparation method disclosed in any one of claims 2 to 3 in preparation of high-performance composite material substrates, high-temperature-resistant coatings and photoelectric materials.
5. The low-temperature cured high-heat-resistance silylbenzyne resin disclosed in claim 1 or prepared by the preparation method disclosed in any one of claims 2-3, and the application of the low-temperature cured high-heat-resistance silylbenzyne resin in the fields of space vehicles and photoelectric materials.
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| EP1355974A1 (en) * | 2000-11-10 | 2003-10-29 | Commissariat A L'Energie Atomique | Poly (ethynylene phenylene ethynylene polysiloxene (silylene)) and methods for preparing same |
| JP2005012138A (en) * | 2003-06-23 | 2005-01-13 | Mitsui Chemicals Inc | High purity metal diffusion barrier film |
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