CN109762010B - Sulfur-containing silicon aryne resin and composite material and preparation method thereof - Google Patents
Sulfur-containing silicon aryne resin and composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a sulfur-containing silicon aryne resin, a composite material thereof and a preparation method thereof. The structural formula is as follows, G is selected from any one of the following groups:
or
R1And R2Independently H, methyl, phenyl, vinyl or ethyl; n is an integer of 1 to 5. The resin is stable and easy to store at normal temperature, can be polymerized, crosslinked and cured at 170-250 ℃, and has excellent mechanical property, thermal stability and thermo-oxidative stability; the decomposition temperature of the condensate in nitrogen is up to 498 ℃, the decomposition temperature in air is up to 497 ℃, and the condensate has high heat resistance and mechanical property. The sulfur-containing silicon aryne resin composite material has the advantages of excellent heat resistance and mechanical property, high bending strength, high bending modulus and high shear strength.
Description
Technical Field
The invention relates to a sulfur-containing silicon aryne resin, a composite material thereof and a preparation method thereof.
Background
The silicon-containing aryne (PSA) resin is aryl polyacetylene resin with a main chain containing silicon elements, is organic and inorganic hybrid resin, can be used as thermosetting resin, and is a resin composite material reinforced by fibers and fabrics thereof, and has excellent heat resistance and mechanical properties, but the silicon-containing aryne resin is brittle after being cured, has slightly insufficient mechanical strength, and limits the application of the silicon-containing aryne resin in the field of aerospace.
Since 2002, Huangrong subject group of Huadong university of Engineers has carried out fundamental 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 are researched and invented, such as Wangman et al (Reactive and Functional Polymers,2011,71: 899-904) which introduce boron element into the structure of the silicon-containing aryne resin, and the silicon-containing aryne resin with high thermal oxidation resistance is invented; high Performance Polymer (2017, 29(5): 595-601) introduces ether bonds into a main chain structure of the silicon-containing aryne resin to prepare the silicon-containing aryne resin with excellent mechanical properties. At present, no research related to the introduction of sulfur element into the traditional silicon-containing aryne resin system exists in the prior art.
Disclosure of Invention
The invention provides a sulfur-containing silicon aryne resin, a composite material thereof and a preparation method thereof. The sulfur-containing silicon aryne resin is a black brown solid, is stable and easy to store at normal temperature, can be polymerized, crosslinked and cured at 170-250 ℃, and has excellent mechanical property, thermal stability and thermo-oxidative stability; the decomposition temperature of the condensate in nitrogen is up to 498 ℃, the decomposition temperature in air is up to 497 ℃, and the condensate has high heat resistance and mechanical property. The sulfur-containing silicon aryne resin composite material has the advantages of excellent heat resistance and mechanical property, high bending strength, high bending modulus and high shear strength. In one embodiment, the bending strength of the carbon fiber reinforced composite material can reach 404.3MPa, and the carbon fiber reinforced composite material is expected to be applied to the high-tech fields such as aerospace and the like.
The invention solves the technical problems through the following technical scheme.
The invention provides a sulfur-containing silicon aryne resin, which has the following structural formula:
wherein G is selected from any one of the following groups: -s-,
or
R1And R2Independently H, methyl, phenyl, vinyl or ethyl;
n is 1 to 5 and is an integer.
In the present invention, n is preferably 1 to 3, such as 1, 2 or 3.
In the present invention, the number average molecular weight Mn of the sulfur-containing silicon aryne resin is preferably 2000 to 3000, more preferably 2000 to 2500, such as 2367, 2011, 2297, 2264, 2498 or 2602.
In the present invention, the weight average molecular weight Mw of the sulfur-containing silicon aryne resin is preferably 2500 to 4500, more preferably 2500 to 4100, such as 3896, 2956, 3834, 3808, 3996 or 4059.
In the present invention, the polydispersity index Mw/Mn of the sulfur-containing aryne resin can be conventional in the art, and is preferably 1 to 1.7, more preferably 1.2 to 1.7, such as 1.65, 1.47, 1.67, 1.68, 1.60 or 1.56.
In the present invention, preferably, G is-S-, R1Is methyl, R2Is phenyl, more preferably, G is-S-, R1Is methyl, R2Is phenyl, Mn ═ 2367, polydispersity index 1.65.
In the present invention, preferably, G is-S-, R1Is methyl, R2Is phenyl, more preferably, G is-S-, R1Is methyl, R2Is phenyl, Mn-2011, polydispersity index 1.47.
In the present invention, preferably, G is-S-, R1Is methyl, R2Is methyl, more preferably, G is-S-, R1Is methyl, R2Is methyl, Mn ═ 2297, polydispersity index 1.67.
In the present invention, preferably, G is-S-, R1Is methyl, R2Is H, more preferably, G is-S-, R1Is methyl, R2H, Mn — 2264, polydispersity index 1.68.
In the present invention, preferably G is
R1Is methyl, R2Is phenyl, more preferably, G is
R1Is methyl, R2Is phenyl, Mn ═ 2498, polydispersity index 1.60.
In the present invention, preferably G is
R1Is methyl, R2Is phenyl, more preferably, G is
R1Is methyl, R2Is phenyl, Mn-2602, polydispersity index 1.56.
The invention also provides a preparation method of the silicon aryne resin (PSFA) containing the thioether structure (PSSA) or the sulfone structure, which comprises the following steps:
1) adding halogenated hydrocarbon into a mixture of magnesium powder and an organic solvent under inert atmosphere to react to generate an alkyl Grignard reagent;
2) adding an alkyne monomer into the alkyl Grignard reagent to react to generate an alkyne Grignard reagent; wherein the alkyne monomer is diacetylene diphenyl sulfide or diacetylene diphenyl sulfone;
3) adding dichlorosilane into the alkyne Grignard reagent to carry out polymerization reaction to obtain the product.
The reaction process is as follows:
1.RBr+Mg→RMgBr
wherein G is selected from-s-or
R1And R2Independently H, methyl, phenyl, vinyl or ethyl, n is 1-5 and is an integer. The G, R1、R2And n are as previously described.
In step 1), the inert atmosphere may be an inert atmosphere which does not participate in chemical reactions, such as a nitrogen atmosphere, obtained by methods conventional in the art.
In step 1), the halogenated hydrocarbon may be conventional in the art, for example, bromoethane.
In step 1), the halogenated hydrocarbon is preferably added in the form of a solution. In the halogenated hydrocarbon solution, the concentration of the halogenated hydrocarbon is preferably 10 to 15mol/L, for example 12 mol/L. In the halogenated hydrocarbon solution, the solvent employed may be conventional in the art, and is typically tetrahydrofuran and/or toluene.
In step 1), the halogenated hydrocarbon is generally slowly added dropwise to the mixture through a constant pressure funnel according to the common knowledge in the art, and the dropping time of the halogenated hydrocarbon can be conventional in the art, and is preferably 10-60 min. The halogenated hydrocarbons are typically subjected to anhydrous treatment prior to use according to methods conventional in the art.
In step 1), the molar ratio of the halogenated hydrocarbon to the magnesium powder may be conventional in the art, and is preferably 1: (1.25-1.5), for example 1: 1.25.
In step 1), the organic solvent may be an organic solvent that is conventional in the art and can be used for performing the grignard reaction, and preferably includes one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane, and toluene. The organic solvent is typically treated anhydrous prior to use according to methods conventional in the art.
In step 1), the reaction may be a condition of a grignard reaction which is conventional in the art. The reaction temperature is preferably 35 to 45 ℃, for example 40 ℃. The reaction time is preferably 1 to 3 hours.
In step 2), the molar ratio of the alkyne monomer to the alkyl halide may be conventional in the art, preferably 1: 2.
in step 2), the alkyne monomer is preferably added in solution. In the alkyne monomer solution, the concentration of the alkyne monomer is preferably 0.25 to 0.85mol/L, for example 0.8 mol/L. In the alkyne monomer solution, the solvent employed may be conventional in the art, and is typically one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene.
In the step 2), preferably, the alkyne monomer is added into the alkyl grignard reagent in a dropwise manner during cooling in an ice-water bath. The dropping time of the alkyne monomer is preferably 0.5 to 2 hours, for example 1.5 hours.
In the step 2), the operation and conditions of the reaction can be conventional in the art, and preferably the reaction is performed under heating and refluxing for 1 to 3 hours, for example, under heating and refluxing for 1.5 hours.
In step 3), the dichlorosilane may be of a kind conventional in the art, and preferably includes one or more of dimethyldichlorosilane, methyldichlorosilane, methylphenyldichlorosilane, methylvinyldichlorosilane, diphenyldichlorosilane, and methylethyldichlorosilane.
In step 3), the dichlorosilane is preferably added in the form of a solution. In the dichlorosilane solution, the concentration of dichlorosilane is preferably 3 to 15mol/L, such as 3mol/L, 4mol/L or 4.5 mol/L. In the dichlorosilane solution, the solvent employed may be conventional in the art, and is typically one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane, and toluene.
In the step 3), preferably, the dichlorosilane is added to the alkyne grignard reagent in a dropwise manner during cooling in an ice-water bath. The dropping time of the dichlorosilane can be conventional in the field, and is preferably 10-60 min.
In the step 3), the molar ratio of the alkyne monomer to the dichlorosilane can be conventional in the art, and is preferably (1-2): 1, e.g., 1.33, 1.5:1 or 2: 1.
in the step 3), the operation and conditions of the polymerization reaction may be conventional in the art, and preferably the heating reflux reaction is performed for 1 to 3 hours, for example, the heating reflux reaction is performed for 1.5 hours.
Preferably, the reaction solution produced by the polymerization reaction in step 3) is subjected to a post-treatment. The post-treatment operation and conditions can be conventional in the art, and generally include removing the solvent, adding the solvent (such as toluene), cooling with an ice water bath, adding the terminating agent, adding a hydrochloric acid aqueous solution with a concentration of 40-60% (such as 50%) to react to remove the residual magnesium powder, washing to be neutral, drying, filtering, removing the solvent, and drying again.
Wherein, the washing is generally repeated to be neutral by using deionized water. The solvent removal operation generally adopts a rotary evaporation method. The terminating agent may be one conventionally used in the art and generally includes one or more of water, acetic acid, and hydrochloric acid.
In the present invention, the above-mentioned silicon aryne resin (PSSA) containing a thioether structure is preferably oxidized to obtain a silicon aryne resin (PSOA) containing a sulfoxide structure. The operation and conditions of the oxidation may be conventional in the art, and are generally performed as follows: adding an oxidant into a silicon aryne resin solution containing a thioether structure for oxidation reaction. The reaction process is as follows:
wherein R is1And R2Independently H, methyl, phenyl, vinyl or ethyl, n is 1-5, andare integers.
The organic solvent used in the solution of the silicon aryne resin containing the thioether structure may be any one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene, which are conventional in the art and can dissolve the silicon aryne resin containing the thioether structure. The concentration of the silicon aryne resin containing thioether structure in the solution of silicon aryne resin containing thioether structure can be conventional in the art, and is preferably 0.2 to 0.5mol/L, such as 0.33 mol/L.
The oxidant can be conventional in the art, and is preferably m-chloroperoxybenzoic acid or hydrogen peroxide.
Wherein, preferably, the oxidant is slowly added into the silicon aryne resin solution containing the thioether structure during the cooling in the ice water bath.
Wherein the molar ratio of the thioether structure-containing silicon aryne resin to the oxidant can be conventional in the art, and is preferably 1: (3-6), for example 1: 3.
The operation and conditions of the oxidation reaction can be conventional in the art, and the reaction is generally carried out at room temperature for 12-24 hours.
Among them, the reaction solution obtained by the oxidation reaction is preferably subjected to a post-treatment. The operations and conditions of the said work-up can be conventional in the art and are preferably carried out as follows: filtering, washing with saturated sodium carbonate for 3-5 times, and washing with deionized water to neutrality, wherein the anhydrous Na is2SO4Drying, filtering, removing solvent, and drying again.
The invention also provides a sulfur-containing silicon aryne resin composite material, and the sulfur-containing silicon aryne resin is adopted as the raw material.
In the present invention, the sulfur-containing silicon aryne resin composite material can be prepared by a method conventional in the art for composite materials, such as a molding method.
The invention also provides a preparation method of the sulfur-containing silicon aryne resin composite material, which comprises the following steps:
1) impregnating a reinforcing fiber with the solution containing the sulfur-containing silicon aryne resin to prepare a prepreg;
2) and removing the solvent from the prepreg, and carrying out mould pressing, curing and forming to obtain the sulfur-containing silicon aryne resin composite material.
In the step 1), the concentration of the sulfur-containing aryne resin in the solution can be conventional in the art, and is preferably 35-40 wt%. The solvent employed in the solution may be conventional in the art and may typically be one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene.
In step 1), the reinforcing fibers may be reinforcing fibers conventionally used in the art for preparing composite materials, and are typically carbon fibers or quartz fibers. The carbon fiber may be a T300 carbon fiber, a T700 carbon fiber, or a T800 carbon fiber.
In step 1), the operation and conditions of the impregnation may be conventional in the art.
In step 2), the prepreg can be stacked to a desired height and then subjected to solvent removal operation, as required.
In step 2), the solvent removal operation and conditions may be conventional in the art and are generally performed in a vacuum oven.
In step 2), the operation and conditions of the press-molding, curing and forming can be conventional in the art and are generally carried out on a press vulcanizer. The temperature of the mould pressing curing molding is preferably 170-300 ℃. The time for the mold pressing, curing and forming is preferably 8-12 hours. The pressure of the mould pressing solidification molding is preferably 0.5-3 MPa. The operation of press-curing molding preferably includes the steps of: and under the pressure of 3MPa, sequentially preserving heat at 180 ℃ for 2h, preserving heat at 220 ℃ for 2h and preserving heat at 260 ℃ for 4h, and then forming.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
the sulfur-containing silicon aryne resin is a black brown solid, is stable and easy to store at normal temperature, can be polymerized, crosslinked and cured at 170-250 ℃, and has excellent mechanical property, thermal stability and thermo-oxidative stability; the decomposition temperature of the condensate in nitrogen is up to 498 ℃, the decomposition temperature in air is up to 497 ℃, and the condensate has high heat resistance and mechanical property.
The sulfur-containing silicon aryne resin composite material has the advantages of excellent heat resistance and mechanical property, high bending strength, high bending modulus and high shear strength. In one embodiment, the bending strength of the carbon fiber reinforced composite material can reach 404.3MPa, and the carbon fiber reinforced composite material is expected to be applied to the high-tech fields such as aerospace and the like.
Drawings
FIG. 1 is a chart of the hydrogen nuclear magnetic resonance spectrum of PSSA-1 resin synthesized in example 1 (1H-NMR)。
FIG. 2 is an infrared spectrum (FTIR) of PSSA-1 resin synthesized in example 1.
FIG. 3 is a TGA graph of a cured PSSA-1 resin synthesized in example 1 in air and nitrogen.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The structure of the synthesized sulfur-containing silicon aryne resin uses hydrogen nuclear magnetic resonance spectrum (1H-NMR) and infrared spectroscopy (FTIR); hydrogen nuclear magnetic resonance spectroscopy (1H-NMR) Using a Bruker AVANCE 500 model 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 a Nicolet 6700 Fourier Infrared Spectroscopy, KBr pellet method, from Nicolet, USA, scanning Range 4000--1Resolution of 0.09cm-1And the number of scanning times is 32.
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 bending properties of the resin composite were tested by a three-point bending method. The mechanical properties of the resin composite material are measured by using a Shenzhen New Miss material detection Limited SANS CMT 4204 type microcomputer-controlled electronic universal tester, 5-10 test sample bars are used in each group, and the results are averaged. The bending strength and the bending modulus of the fiber cloth reinforced resin composite material flat plate are tested according to GB/T1499-2005, the experimental loading speed is 2mm/min, and the test sample is continuously loaded to be damaged during the experiment. 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.
Example 1
Synthesis of thioether-containing silicon-containing aryne resin PSSA-1
1) Under the nitrogen atmosphere, adding 0.300mol of magnesium powder and 60mL of tetrahydrofuran into a 500mL four-neck flask provided with a stirrer, a constant pressure funnel, a thermometer and a condenser, slowly dropwise adding a mixed solution of 0.240mol of bromoethane and 20mL of tetrahydrofuran through the constant pressure funnel in an ice water bath for about 10min, and reacting at 40 ℃ for 1h after the dropwise adding is finished to prepare a gray ethyl Grignard reagent;
2) cooling the reaction liquid to below room temperature by adopting an ice water bath, adding a mixed solution of 0.120mol of 4, 4' -diacetylene diphenyl sulfide and 150mL of tetrahydrofuran (in the mixed solution, the concentration of an alkyne monomer is 0.8mol/L), dropwise adding for 0.5h, discharging gas after the reaction is finished, and carrying out reflux reaction for 1.5h at 70 ℃;
3) cooling the reaction liquid to below room temperature, adding a mixed solution of 0.080mol of methyl phenyl dichlorosilane and 20mL of tetrahydrofuran through a constant pressure funnel, dropwise adding for about 10min, and carrying out reflux reaction at 70 ℃ for 1.5h after dropwise adding; the specific reaction flow is as follows:
1.RBr+Mg→RMgBr
wherein G is-S-and R1Is methyl, R2Is phenyl, n is 2.
4) After most of tetrahydrofuran was distilled off from the obtained solution, 200mL of toluene was added to the reaction system, the reaction mixture was cooled to room temperature or lower, a mixed solution of 0.240mol of glacial acetic acid and 20mL of toluene was added dropwise to terminate the reaction, and 50mL (25%) of a 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 4 hours to obtain the PSSA-1 resin, wherein the yield is 95%, the resin is a dark brown solid, and the melting range is 88-94 ℃.
FIG. 1 is a chart of the hydrogen nuclear magnetic resonance spectrum of PSSA-1 resin synthesized in example 11H-NMR(CDCl3). As is clear from FIG. 1, the solvent peak was found at 7.26ppm, the proton peak of ≡ C-H was found at 3.05ppm, and Si-CH was found at 0.48ppm3The multiple peak at 6.91-7.49 ppm is the proton peak on the benzene ring, and the equivalent to C-H and Si-CH3The proton peak relative integral area ratio of (a) is 1.0:3.2, which is close to the theoretical value of 1.0: 3.0.
FIG. 2 is an infrared spectrum (FTIR) of PSSA-1 resin synthesized in example 1. As can be seen from FIG. 2, 3280cm-1The asymmetric stretching vibration peak of terminal alkyne hydrogen is positioned; 2962cm-1Is of the formula-CH3The stretching vibration peak of (1); 2162cm-1Is a stretching vibration peak of alkynyl-C.ident.C-; 1179cm-1Is the stretching vibration peak of C-S on the aromatic ring.
After PSSA-1 prepared in example 1 is cured under the conditions of 170 ℃/curing 2h +210 ℃/curing 2h +250 ℃/curing 4h, a dense and bright black cured product is obtained, and is ground into powder for thermogravimetric analysis. FIG. 3 is a TGA plot in air and nitrogen of the product resulting from the curing of PSSA-1 synthesized in example 1. As can be seen from FIG. 3, in the nitrogen atmosphere, the weight loss 5% temperature was 498 ℃ and the 800 ℃ residual rate was 78.6%; under the air atmosphere, the temperature of 5 percent of weight loss is 497 ℃, and the residual rate at 800 ℃ is 18.3 percent.
A cured resin casting was prepared from PSSA-1 obtained in example 1, and the method for preparing the cured resin casting was as follows: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; then the mould is placed at 180 ℃ and 160 DEG CPreheating for 2 hours in a vacuum oven. Pouring the PSEA-P2-1 resin into a mold, after the resin is molten, keeping the resin under vacuum for about 0.5h to remove air and solvent until no air bubbles appear within 3s, and then transferring the resin into a high-temperature oven for curing. The curing process comprises the following steps: 170 ℃/curing for 2h +210 ℃/curing for 2h +250 ℃/curing for 4 h. And demolding after curing is finished, and polishing the sample strip to a test standard size. Bending property test specimen size: 80X 15X 4mm3. The bending property of the cured product of the PSSA-1 resin casting body is tested by a three-point bending test method, and the result shows that the bending strength is 34.8MPa and the bending modulus is 2.3 GPa.
Example 2
Synthesis of thioether-containing silicon-containing aryne resin PSSA-2
1) Under the nitrogen atmosphere, adding 0.300mol of magnesium powder and 60mL of tetrahydrofuran into a 500mL four-neck flask provided with a stirrer, a constant pressure funnel, a thermometer and a condenser, slowly dropwise adding a mixed solution of 0.240mol of bromoethane and 20mL of tetrahydrofuran through the constant pressure funnel in an ice water bath for about 10min, and reacting at 40 ℃ for 1h after the dropwise adding is finished to prepare a gray ethyl Grignard reagent;
2) cooling the reaction liquid to below room temperature by adopting an ice water bath, adding a mixed solution of 0.120mol of 4, 4' -diacetylene diphenyl sulfide and 150mL of tetrahydrofuran (in the mixed solution, the concentration of an alkyne monomer is 0.8mol/L), dropwise adding for 0.5h, discharging gas after the reaction is finished, and carrying out reflux reaction for 1.5h at 70 ℃;
3) cooling the reaction liquid to below room temperature, adding a mixed solution of 0.060mol of methyl phenyl dichlorosilane and 20mL of tetrahydrofuran through a constant pressure funnel, dropwise adding for about 10min, and carrying out reflux reaction at 70 ℃ for 1.5h after dropwise adding; the reaction scheme of this example is as in example, the product has the same structural formula as example 1, and the repeating unit n is 1.
4) After most of tetrahydrofuran was distilled off from the obtained solution, 200mL of toluene was added to the reaction system, the reaction mixture was cooled to room temperature or lower, a mixed solution of 0.240mol of glacial acetic acid and 20mL of toluene was added dropwise to terminate the reaction, and 50mL (25%) of a hydrochloric acid solution was added dropwise to the flask. The reaction solution was transferred to a 1000mL separatory funnel, washed with deionized water to near neutrality, and the upper organic phase was separated,adding anhydrous Na2SO4Drying, filtering, distilling under reduced pressure to remove the solvent, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain the PSSA-2 resin, wherein the yield is 95%, the resin is a dark brown solid, and the melting range is 72-85 ℃.
Of PSSA-2 resins1H-NMR(CDCl3) And (3) analysis: a solvent peak at 7.26ppm, a proton peak of ≡ C-H at 3.02ppm, and Si-CH at 0.47ppm3The multiple peak at 6.90-7.52 ppm is the proton peak on the benzene ring, and the equivalent to C-H and Si-CH3The proton peak relative integral area ratio of (a) is 1.0:2.1, which is close to the theoretical value of 1.0: 2.0.
FTIR analysis of PSSA-2 resin: 3279cm-1The asymmetric stretching vibration peak of terminal alkyne hydrogen is positioned; 3012cm-1Is of the formula-CH3The stretching vibration peak of (1); 2202cm in length-1Is a stretching vibration peak of alkynyl-C.ident.C-; 1180cm-1Is the stretching vibration peak of C-S on the aromatic ring.
After the PSSA-2 prepared in the example 2 is cured under the conditions of 170 ℃/curing 2h +210 ℃/curing 2h +250 ℃/curing 4h, a compact and bright black cured substance is obtained, and the powder is ground into powder for thermogravimetric analysis. Performing thermal weight loss analysis on the cured product, wherein the temperature of 5% weight loss is 467 ℃ and the residual rate of 74.5% at 800 ℃ in a nitrogen atmosphere; under the air atmosphere, the weight loss 5% temperature is 460 ℃, and the residual rate at 800 ℃ is 16.7%.
A cured resin casting was prepared from the product obtained in example 2 under the conditions disclosed in example 1. The bending property of the cured resin casting body is tested by a three-point bending test method, and the result shows that the bending strength is 26.1MPa and the bending modulus is 2.6 GPa.
Example 3
Synthesis of thioether-containing silicon-containing aryne resin PSSA-3
1) Under the nitrogen atmosphere, adding 0.300mol of magnesium powder and 60mL of tetrahydrofuran into a 500mL four-neck flask provided with a stirrer, a constant pressure funnel, a thermometer and a condenser, slowly dropwise adding a mixed solution of 0.240mol of bromoethane and 20mL of tetrahydrofuran through the constant pressure funnel in an ice water bath for about 10min, and reacting at 40 ℃ for 1h after the dropwise adding is finished to prepare a gray ethyl Grignard reagent;
2) cooling the reaction liquid to below room temperature by adopting an ice water bath, adding a mixed solution of 0.120mol of 4, 4' -diacetylene diphenyl sulfide and 150mL of tetrahydrofuran (in the mixed solution, the concentration of an alkyne monomer is 0.8mol/L), dropwise adding for 0.5h, discharging gas after the reaction is finished, and carrying out reflux reaction for 1.5h at 70 ℃;
3) cooling the reaction liquid to below room temperature, adding a mixed solution of 0.090mol of dimethyldichlorosilane and 20mL of tetrahydrofuran through a constant pressure funnel, dropwise adding for about 10min, and carrying out reflux reaction at 70 ℃ for 1.5h after dropwise adding;
4) after most of tetrahydrofuran was distilled off from the obtained solution, 200mL of toluene was added to the reaction system, the reaction mixture was cooled to room temperature or lower, a mixed solution of 0.240mol of glacial acetic acid and 20mL of toluene was added dropwise to terminate the reaction, and 50mL (25%) of a 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 solvent, and drying in a vacuum oven at 60 deg.C for 4h to obtain PSSA-3 resin with yield of 95% as orange yellow solid. The product has the following structural formula:
Of PSSA-3 resins1H-NMR(CDCl3) And (3) analysis: a solvent peak at 7.26ppm, a proton peak of ≡ C-H at 3.12ppm, and Si-CH at 0.47ppm3The multiple peak at 7.25-7.43 ppm is the proton peak on the benzene ring, and the equivalent to C-H and Si-CH3The proton peak relative integral area ratio of (A) is 1.0:3.1, which is close to the theoretical value of 1.0: 3.0.
FTIR analysis of PSSA-3 resin: 3280cm-1The asymmetric stretching vibration peak of terminal alkyne hydrogen is positioned; 3010cm-1Is of the formula-CH3The stretching vibration peak of (1); 2201cm-1Is a stretching vibration peak of alkynyl-C.ident.C-; 1180cm-1Is the stretching vibration peak of C-S on the aromatic ring。
After the PSSA-3 resin is cured at the conditions of 170 ℃/2h +210 ℃/2h +250 ℃/4h, a compact and bright black cured material is obtained,
after the PSSA-3 prepared in example 3 is cured under the conditions of 170 ℃/curing 2h +210 ℃/curing 2h +250 ℃/curing 4h, a compact and bright black cured product is obtained, and is ground into powder for thermogravimetric analysis. The thermal weight loss analysis of the condensate is carried out, and the temperature of 5 percent weight loss is 419 ℃ and the residual rate of 800 ℃ is 68.7 percent under the nitrogen atmosphere.
Example 4
Synthesis of thioether-containing silicon-containing aryne resin PSSA-4
1) Under the nitrogen atmosphere, adding 0.300mol of magnesium powder and 60mL of methyl tetrahydrofuran into a 500mL four-neck flask provided with a stirrer, a constant pressure funnel, a thermometer and a condenser, slowly dropwise adding a mixed solution of 0.240mol of bromoethane and 20mL of methyl tetrahydrofuran through the constant pressure funnel in an ice water bath for about 10min, and reacting at 40 ℃ for 1h after the dropwise adding is finished to prepare a gray ethyl Grignard reagent;
2) cooling the reaction liquid to below room temperature by adopting an ice water bath, adding a mixed solution of 0.120mol of 4, 4' -diacetylene diphenyl sulfide and 150mL of methyl tetrahydrofuran (in the mixed solution, the concentration of an alkyne monomer is 0.8mol/L), dropwise adding for 0.5h, discharging gas after the reaction is finished, and carrying out reflux reaction for 1.5h at 70 ℃;
3) cooling the reaction liquid to below room temperature, adding a mixed solution of 0.090mol of methyl (hydrogen) dichlorosilane and 20mL of methyl tetrahydrofuran through a constant pressure funnel, dropwise adding for about 10min, and carrying out reflux reaction at 70 ℃ for 1.5h after dropwise adding;
4) after most of methyltetrahydrofuran was distilled off from the obtained solution, 200mL of toluene was added to the reaction system, the reaction mixture was cooled to room temperature or lower, a mixed solution of 0.240mol of glacial acetic acid and 20mL of toluene was added dropwise to terminate the reaction, and 50mL (25%) of a 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 solvent, and drying in a vacuum oven at 60 deg.C for 4 hr to obtain PSSA-4 resin, 95% yield, resin as yellow solid. The product has the following structural formula:
Of PSSA-4 resin1H-NMR(CDCl3) And (3) analysis: a solvent peak at 7.26ppm, a proton peak of ≡ C-H at 3.12ppm, and Si-CH at 0.53ppm34.62ppm of the proton peak of Si-H, and 7.24-7.43 ppm of the multiplet of the proton peak of benzene ring, wherein ≡ C-H and Si-CH3The proton peak relative integral area ratio of (a) is 1.0:3.3, which is close to the theoretical value of 1.0: 3.0.
FTIR analysis of PSSA-4 resin: 3282cm-1The asymmetric stretching vibration peak of terminal alkyne hydrogen is positioned; 3020cm-1Is of the formula-CH3The stretching vibration peak of (1); 2221cm-1Is a stretching vibration peak of alkynyl-C.ident.C-; 1180cm-1Is the stretching vibration peak of C-S on the aromatic ring.
After the PSSA-4 resin is cured at the conditions of 170 ℃/2h +210 ℃/2h +250 ℃/4h, a compact and bright black cured material is obtained,
the PSSA-4 prepared in example 4 was cured at 170 ℃/2h +210 ℃/2h +250 ℃/4h to obtain a dense and bright black cured product, which was ground into a powder for thermogravimetric analysis. The thermal weight loss analysis is carried out on the cured product, and the temperature of 5 percent weight loss is 528 ℃ and the residual rate of 800 ℃ is 82.3 percent under the nitrogen atmosphere.
Example 5
Synthesis of sulfoxide-containing silicon-containing aryne resin PSOA
Adding 0.10mol of PSSA-1 resin and 300mL of dichloromethane into a 500mL four-neck flask provided with a stirrer, a thermometer and a condenser tube, slowly adding 0.30mol of m-chloroperoxybenzoic acid (m-CPBA) under an ice-water bath, reacting at room temperature for 12 hours, transferring the obtained solution into a 500mL separating funnel, washing the solution for multiple times by using saturated potassium carbonate solution, washing the solution to be neutral by using deionized water, adding anhydrous Na2SO4Drying and filteringAnd distilling under reduced pressure to remove the solvent, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain the PSOA resin, wherein the yield is 85 percent, the resin is yellow solid, and the melting range is 113-116 ℃.
The product has the following structural formula:
Of PSOA resin1H-NMR(CDCl3) And (3) analysis: a solvent peak at 7.26ppm, a proton peak of ≡ C-H at 3.17ppm, and Si-CH at 0.69ppm3The multiple peak at 7.44-7.87 ppm is the proton peak on the benzene ring, and the equivalent to C-H and Si-CH3The proton peak relative integral area ratio of (a) is 1.0:3.2, which is close to the theoretical value of 1.0: 3.0.
FTIR analysis of PSOA resin: 3283cm-1The asymmetric stretching vibration peak of terminal alkyne hydrogen is positioned; 3051cm-1Is of the formula-CH3The stretching vibration peak of (1); 2159cm-1Is a stretching vibration peak of alkynyl-C.ident.C-; 1050cm-1The peak is the stretching vibration peak of sulfoxide.
The PSOA prepared in the example 5 is cured under the conditions of 170 ℃/curing for 2h +210 ℃/curing for 2h +250 ℃/curing for 4h to obtain a dense and bright black cured product, and the dense and bright black cured product is ground into powder for thermogravimetric analysis. Performing thermal weight loss analysis on the cured product, wherein the temperature of 5 percent of weight loss is 449 ℃ and the residual rate at 800 ℃ is 75.6 percent under the nitrogen atmosphere; under the air atmosphere, the temperature of 5 percent of weight loss is 431 ℃ and the residual rate at 800 ℃ is 14.6 percent.
A cured resin casting was prepared from the product obtained in example 5 under the conditions disclosed in example 1. The cured resin casting body is tested by a three-point bending test method, and the result shows that the bending strength is 36.2MPa and the bending modulus is 2.7 GPa.
Example 6
Synthesis of sulfone-containing silicon-containing aryne resin PSFA
1) Under the nitrogen atmosphere, adding 0.300mol of magnesium powder and 60mL of tetrahydrofuran into a 500mL four-neck flask provided with a stirrer, a constant pressure funnel, a thermometer and a condenser, slowly dropwise adding a mixed solution of 0.240mol of bromoethane and 20mL of tetrahydrofuran through the constant pressure funnel in an ice water bath for about 10min, and reacting at 40 ℃ for 1h after the dropwise adding is finished to prepare a gray ethyl Grignard reagent;
2) cooling the reaction liquid to below room temperature by adopting an ice water bath, adding a mixed solution of 0.120mol of 4, 4' -diacetylene diphenyl sulfone and 150mL of tetrahydrofuran (in the mixed solution, the concentration of the alkyne monomer is 0.8mol/L), dropwise adding for 0.5h, discharging gas after the reaction is finished, and carrying out reflux reaction for 1.5h at 70 ℃;
3) cooling the reaction liquid to below room temperature, adding a mixed solution of 0.080mol of methyl phenyl dichlorosilane and 20mL of tetrahydrofuran through a constant pressure funnel, dropwise adding for about 10min, and carrying out reflux reaction at 70 ℃ for 1.5h after dropwise adding;
4) after most of tetrahydrofuran was distilled off from the obtained solution, 200mL of toluene was added to the reaction system, the reaction mixture was cooled to room temperature or lower, a mixed solution of 0.240mol of glacial acetic acid and 20mL of toluene was added dropwise to terminate the reaction, and 50mL (25%) of a 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 PSFA resin, wherein the yield is 95%, the resin is a black brown solid, and the melting range is 120-130 ℃.
The product has the following structural formula:
Of PSFA resin1H-NMR(CDCl3) And (3) analysis: at 7.26ppm is solventPeak, 3.25ppm as the proton peak of ≡ C-H, 0.71ppm as Si-CH3The multiple peak at 7.43-8.06 ppm is the proton peak on the benzene ring, and the equivalent to C-H and Si-CH3The proton peak relative integral area ratio of (a) is 1.0:3.3, which is close to the theoretical value of 1.0: 3.0.
FTIR analysis of PSFA resin: 3278cm-1The asymmetric stretching vibration peak of terminal alkyne hydrogen is positioned; 3066cm-1Is of the formula-CH3The stretching vibration peak of (1); 2161cm-1Is a stretching vibration peak of alkynyl-C.ident.C-; 1300cm-1Is the stretching vibration peak of sulfone.
The product obtained in the example 6 is solidified under the conditions of 170 ℃/solidification for 2h +210 ℃/solidification for 2h +250 ℃/solidification for 4h to obtain a compact and bright black solidified substance, and the solidified substance is ground into powder for thermogravimetric analysis. Performing thermal weight loss analysis on the condensate, wherein the temperature of 5% weight loss is 376 ℃ and the residual rate of 800 ℃ is 65.0% under the nitrogen atmosphere; under the air atmosphere, the weight loss 5% temperature is 380 ℃, and the residual rate at 800 ℃ is 12.6%.
A cured resin casting was prepared from the product obtained in example 6 under the conditions disclosed in example 1. The bending property of the cured resin casting body is tested by a three-point bending test method, and the result shows that the bending strength is 40.5MPa and the bending modulus is 2.8 GPa.
Example 7
Preparation of sulfur-containing silicon aryne resin composite material
Three kinds of sulfur-containing aryne resins (PSSA-1, PSOA, product PSFA, product PSOA, product2The 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 (3) placing the prepreg on a flat vulcanizing machine, and sequentially carrying out temperature rise procedures of 170 ℃/curing for 2h +210 ℃/curing for 2h +250 ℃/curing for 4h under the pressure of 3MPa to prepare the sulfur-containing silicon aryne resin composite plate with the size of 15cm multiplied by 10cm multiplied by 2 cm.
The mechanical properties of the resin composites prepared from the resins obtained in examples 1, 5 and 6 were measured by a three-point bending method, and the specific test results are shown in table 1. The result shows that the sulfur-containing silicon aryne resin composite material has better mechanical property and can be expected to be used in high and new technical fields of aerospace and the like.
TABLE 1 mechanical Properties of T300/Sulfur-containing Silene aryne resin composites
Remarking: the reinforcing fiber designated by T300 is T300 carbon fiber. The flexural strength and complete modulus tests require specimen dimensions of 45X 15X 2mm3The interlaminar shear test requires a specimen size of 20X 6X 2mm3. The mechanical properties of the resin composite materials prepared from the resins obtained in examples 2-4 are equivalent to those of T300/PSSA-1 in Table 1.
Table 2 shows the Mn, Mw and polydispersity index of the products of examples 1-6. In the GPC measurement, polystyrene was used as an internal standard. Relative molecular weight (GPC) test instrument: waters model 1515 gel permeation chromatograph, Waters corporation, USA; test conditions and methods: tetrahydrofuran was used as the extract at a flow rate of 1 mL/min.
TABLE 2
Claims (16)
1. A sulfur-containing silicon aryne resin, which is characterized by having a structural formula as follows:
wherein G is-S-or
R1Is methyl;
R2is phenyl;
n is 1 to 5 and is an integer.
2. The sulfur-containing silicon aryne resin of claim 1 wherein n is 1, 2 or 3;
or the number average molecular weight of the sulfur-containing silicon aryne resin is Mn of 2000-3000;
or the weight average molecular weight Mw of the sulfur-containing silicon aryne resin is 2500-4500;
or the polydispersity index of the sulfur-containing silicon aryne resin is 1-1.7.
3. The sulfur-containing silicon aryne resin according to claim 1, wherein the number average molecular weight of the sulfur-containing silicon aryne resin is Mn of 2000 to 2500;
or the weight average molecular weight Mw of the sulfur-containing silicon aryne resin is 2500-4100;
or the polydispersity index of the sulfur-containing silicon aryne resin is 1.2-1.7.
4. The sulfur-containing silicon aryne resin of claim 1 wherein the sulfur-containing silicon aryne resin has a number average molecular weight Mn of 2367, 2011, 2297, 2264, 2498 or 2602;
or, the weight average molecular weight of the sulfur-containing silicon aryne resin is 3896, 2956, 3834, 3808, 3996 or 4059;
alternatively, the sulfur-containing silicon aryne resin has a polydispersity index of 1.65, 1.47, 1.67, 1.68, 1.60, or 1.56.
5. The sulfur-containing silicon aryne resin of claim 1 wherein G is-S-, Mn 2367, polydispersity index is 1.65;
or, G is-S-, Mn ═ 2011, polydispersity index 1.47;
or, G is
Mn 2498, polydispersity index 1.60.
6. The preparation method of the sulfur-containing silicon aryne resin is characterized by comprising the following steps of:
1) adding halogenated hydrocarbon into a mixture of magnesium powder and an organic solvent under inert atmosphere to react to generate an alkyl Grignard reagent;
2) adding an alkyne monomer into the alkyl Grignard reagent to react to generate an alkyne Grignard reagent; wherein the alkyne monomer is diethynyl diphenyl sulfide;
3) adding methyl phenyl dichlorosilane into the alkyne Grignard reagent to carry out polymerization reaction to obtain the sulfur-containing silicon aryne resin, wherein the structural formula of the sulfur-containing silicon aryne resin is as follows:
wherein G is-S-; r1Is methyl, R2Is phenyl, n is 1-5 and is an integer.
7. The method for producing a sulfur-containing silicon aryne resin according to claim 6, wherein n is as defined in claim 2;
and/or, in the step 1), the inert atmosphere is a nitrogen atmosphere;
and/or, in step 1), the halogenated hydrocarbon is bromoethane;
and/or, in step 1), the halogenated hydrocarbon is added in the form of a solution; in the halogenated hydrocarbon solution, the concentration of the halogenated hydrocarbon is 10-15 mol/L; in the halogenated hydrocarbon solution, the adopted solvent is tetrahydrofuran and/or toluene;
and/or in the step 1), the dropping time of the halogenated hydrocarbon is 10-60 min;
and/or, in the step 1), the molar ratio of the halogenated hydrocarbon to the magnesium powder is 1: (1.25-1.5);
and/or, in the step 1), the organic solvent is one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene;
and/or in the step 1), the reaction temperature is 35-45 ℃;
and/or in the step 1), the reaction time is 1-3 h.
8. The method for producing a sulfur-containing silicon aryne resin according to claim 7, wherein in the step 1), the concentration of the halogenated hydrocarbon in the halogenated hydrocarbon solution is 12 mol/L;
and/or, in step 1), the temperature of the reaction is 40 ℃.
9. The method of preparing a sulfur-containing silicon aryne resin according to claim 6 wherein the molar ratio of alkyne monomer to halogenated hydrocarbon is from 1: 2;
and/or, in step 2), the alkyne monomer is added in the form of a solution; in the alkyne monomer solution, the concentration of the alkyne monomer is 0.25-0.85 mol/L; in the alkyne monomer solution, the adopted solvent is one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene;
and/or, in the step 2), under the cooling of an ice-water bath, adding the alkyne monomer into the alkyl Grignard reagent in a dropwise manner; the dripping time of the alkyne monomer is 0.5-2 h;
and/or in the step 2), the reaction is a heating reflux reaction for 1-3 h;
and/or, in step 3), the methylphenyldichlorosilane is added in the form of a solution; in the solution of the methyl phenyl dichlorosilane, the concentration of the methyl phenyl dichlorosilane is 3-15 mol/L; in the methyl phenyl dichlorosilane solution, the adopted solvent is one or more of tetrahydrofuran, methyl tetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene;
and/or, in the step 3), under the cooling of an ice-water bath, adding the methyl phenyl dichlorosilane into the alkyne Grignard reagent in a dropwise manner; the dripping time of the methyl phenyl dichlorosilane is 10-60 min;
and/or the molar ratio of the alkyne monomer to the methyl phenyl dichlorosilane is (1-2): 1;
and/or in the step 3), the polymerization reaction is a heating reflux reaction for 1-3 h.
10. The method for producing a sulfur-containing silicon aryne resin according to claim 9, wherein in the step 2), the concentration of the alkyne monomer in the alkyne monomer solution is 0.8 mol/L;
and/or, in the step 2), the reaction is a heating reflux reaction for 1.5 h;
and/or in the step 3), the concentration of the methyl phenyl dichlorosilane in the methyl phenyl dichlorosilane solution is 3mol/L, 4mol/L or 4.5 mol/L;
and/or, in step 3), the molar ratio of alkyne monomer to the methylphenyldichlorosilane is 1.33, 1.5:1, or 2: 1;
and/or, in the step 3), the polymerization reaction is a heating reflux reaction for 1.5 h.
11. The method for producing a sulfur-containing silicon aryne resin according to claim 6, wherein when G is-S-, the sulfur-containing silicon aryne resin is oxidized to obtain a silicon aryne resin having a sulfoxide structure; the oxidation operation comprises the following steps: adding an oxidant into the sulfur-containing silicon aryne resin solution for oxidation reaction;
in the sulfur-containing silicon aryne resin solution, the adopted solvent is one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene;
in the sulfur-containing silicon aryne resin solution, the concentration of the sulfur-containing silicon aryne resin is 0.2-0.5 mol/L;
the oxidant is m-chloroperoxybenzoic acid or hydrogen peroxide;
slowly adding the oxidant into the sulfur-containing silicon aryne resin solution under the cooling of ice-water bath;
the molar ratio of the sulfur-containing silicon aryne resin to the oxidant is 1: (3-6);
the oxidation reaction is carried out for 12-24 hours at room temperature.
12. The method for producing the sulfur-containing silicon aryne resin according to claim 11, wherein the concentration of the sulfur-containing silicon aryne resin in the solution of the sulfur-containing silicon aryne resin is 0.33 mol/L.
13. A sulfur-containing silicon aryne resin composite material, which is prepared from the sulfur-containing silicon aryne resin as claimed in any one of claims 1 to 5.
14. A method for preparing the sulfur-containing silicon aryne resin composite material according to claim 13, comprising the steps of:
1) impregnating a reinforcing fiber with the solution containing the sulfur-containing silicon aryne resin to prepare a prepreg;
2) and removing the solvent from the prepreg, and carrying out mould pressing, curing and forming to obtain the sulfur-containing silicon aryne resin composite material.
15. The method for preparing the sulfur-containing silicon aryne resin composite material according to claim 14, wherein in the step 1), the concentration of the sulfur-containing silicon aryne resin in the solution is 35 to 40 wt%;
and/or, in the step 1), the solvent adopted in the solution is one or more of tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, dichloromethane and toluene;
and/or, in the step 1), the reinforcing fiber is carbon fiber or quartz fiber; the carbon fiber is T300 carbon fiber, T700 carbon fiber or T800 carbon fiber;
and/or in the step 2), the temperature of mould pressing, curing and forming is 170-300 ℃;
and/or in the step 2), the time for mould pressing, curing and forming is 8-12 h;
and/or in the step 2), the pressure of the mould pressing, curing and forming is 0.5-3 MPa.
16. The method of preparing a sulfur-containing silicon aryne resin composite material according to claim 14, wherein said operation of press curing molding comprises the steps of: and under the pressure of 3MPa, sequentially preserving heat at 180 ℃ for 2h, preserving heat at 220 ℃ for 2h and preserving heat at 260 ℃ for 4h, and then forming.
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