CN115894940A - Preparation method of single-source ultrahigh-temperature ceramic precursor containing Zr-C-Si main chain - Google Patents
Preparation method of single-source ultrahigh-temperature ceramic precursor containing Zr-C-Si main chain Download PDFInfo
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Abstract
The invention relates to a preparation method of a single-source ultrahigh-temperature ceramic precursor containing a Zr-C-Si main chain, which comprises the following molecular chain structures:
the main chain structural unit is Zr-C-Si, n represents the degree of polymerization, and the preparation method comprises the following steps: first of all with Cp 2 ZrCl 2 Formation of low oxidation state Cp with reducing metal Mg 2 Zr (II) equivalent active species, followed by addition of (CH) 3 ) 2 Si(CH 2 Cl) 2 And copolymerizing at 110 ℃, filtering to remove a reaction by-product magnesium salt, concentrating in vacuum, and removing the solvent to obtain the orange-yellow polyzirconium carbosilane precursor. The preparation method has novel scheme and simple equipment and process, the obtained precursor can be dissolved in organic solvents such as toluene, THF and the like, the softening point is 140-185 ℃, and good dissolving and melting properties are helpful for later useMolding and processing and functional application.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a preparation method of a single-source ultrahigh-temperature ceramic precursor containing a Zr-C-Si main chain.
Background
The ultrahigh temperature resistant ceramic has excellent performances of high temperature resistance, oxidation resistance, high strength and the like, is a candidate structural material for service in an ultrahigh temperature environment with high competitiveness, and has wide application prospects in the fields of aerospace, nuclear energy and the like. However, the low-temperature oxidation product of the binary ultrahigh-temperature ceramic has a loose and porous structure, and cannot prevent oxygen from permeating, so that the application of the binary ultrahigh-temperature ceramic as a high-temperature structural material is limited. The preparation of the complex phase ceramic by introducing Si element into the ceramic to form a reinforcing phase is an important means for improving the oxidation resistance of the ultrahigh temperature ceramic.
The preparation method of the ultrahigh-temperature ceramic material mainly comprises a Hot Pressing (HP) technology, plasma spark sintering (SPS), a Chemical Vapor Deposition (CVD) method and a precursor conversion method (PDCs). Among them, the precursor conversion method can obtain various ceramic systems with uniform dispersion phase, specific microstructure and performance by molecular design, thus receiving wide attention.
The existing synthesis of the Si-containing single-source ultrahigh-temperature ceramic precursor mainly comprises two schemes of side chain grafting and monomer copolymerization.
The side chain grafting is mainly to use refractory metal M (M = Zr, hf, ta, ti) organic compound to chemically modify Si-containing polymers such as polycarbosilane and the like, and then ceramic to obtain MC (N)/SiC complex phase ceramic, but the scheme has the defects of limited introduction amount of refractory metal M, large side group volume, influence on precursor dissolution and melting performance and the like, and further limits the functional application of the precursor and the ultrahigh temperature resistance of the ceramic.
The monomer copolymerization method is a method for copolymerizing refractory metal M source monomers and Si source monomers, the method simultaneously introduces refractory metal M and an antioxidant component Si into a polymer main chain through copolymerization reaction, the content of M and Si is ensured, a synthesized polymer precursor has certain linearity, and the polymer precursor has good dissolution and melting properties by regulating and controlling reaction conditions and side chain modification, so that the subsequent processing molding and functional application are facilitated.
Disclosure of Invention
The invention provides a preparation method of a Zr-C-Si main chain single-source ultrahigh-temperature ceramic precursor, wherein the single source refers to that the ultrahigh-temperature ceramic precursor is a polymer precursor with a single molecular structure, and the main chain refers to a Zr-C-Si chain segment with the single molecular structure. The preparation method of the invention belongs to the monomer copolymerization method, and simultaneously introduces Zr and Si into a polymer main chain, wherein the introduction of a flexible chain segment Si can effectively regulate and control the flexibility of a Zr-C structure molecular chain, so that the preparation method is expected to prepare the ultrahigh-temperature ceramic fiber.
The invention adopts the technical scheme that the single-source ultrahigh-temperature ceramic precursor containing the Zr-C-Si main chain comprises the following molecular chain structure:
the precursor structure unit is a Zr-C-Si chain, n represents the degree of polymerization, and the ultra-high temperature means that the use temperature of the ceramic obtained by the Zr-C-Si main chain single-source ultra-high temperature ceramic precursor is more than 1600 ℃; the softening point of the Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor is 140-185 ℃.
More importantly, the invention provides a preparation method of the Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor, which comprises the following steps:
s1, preparation of Cp 2 Zr (ii) equivalent active species: cp is 2 ZrCl 2 Adding Mg chips into a first reaction solvent according to a predetermined molar ratio, fully stirring, reacting at room temperature-60 ℃ for 1-6 h, cooling to room temperature, filtering to remove excessive reactant magnesium chips, and obtaining black-purple Cp 2 Zr (II) equivalent active species solution;
s2, preparing a PZCS ceramic precursor: at Cp 2 Adding a certain proportion of ClCH into Zr (II) solution 2 Si(CH 3 ) 2 CH 2 And uniformly stirring Cl and a second reaction solvent at room temperature, heating to 110-130 ℃, reacting, keeping the temperature for 4-24 hours, naturally cooling to room temperature, filtering to remove magnesium salt, and concentrating in vacuum to obtain orange ultrahigh-temperature ceramic precursor powder containing a Zr-C-Si main chain structure.
Further, in step S1, cp 2 ZrCl 2 Molar ratio to Mg chips =1: (2-6).
Further, in step S1, cp 2 ZrCl 2 Molar ratio to Mg chips =1:6.
further, in step S1, the first reaction solvent is anhydrous THF or anhydrous DMF.
Further, in step S2, the second reaction solvent is one of toluene, xylene, and DMF.
Further, in step S2, cp 2 Zr (II) active species and ClCH 2 Si(CH 3 ) 2 CH 2 The molar ratio of the Cl monomer is 5 (4-6).
Further, in step S2, cp 2 Zr (II) active species and ClCH 2 Si(CH 3 ) 2 CH 2 The molar ratio of Cl monomer was 5.
Further, the second solvent is added in one of the following ways:
a. when the second reaction solvent and the first reaction solvent are the same substance, a certain proportion of (CH) is directly dripped 3 ) 2 Si(CH 2 Cl) 2 Fully stirring the monomers, and heating to 110-130 ℃ for copolymerization;
b. when the second reaction solvent is different from the first reaction solvent, cp is 2 Putting the Zr (II) active species solution into a three-neck flask, and carrying out vacuum concentration at room temperature to remove a first reaction solvent not less than 1/3; using dropping funnel to the remaining Cp 2 Injecting a second reaction solvent into the Zr (II) active species solution, and stirring to ensure that Cp is 2 Zr (II) active species solution is evenly dispersed in the mixed solvent, and then a reaction monomer (CH) is slowly dripped into the solution by a disposable injector 3 ) 2 Si(CH 2 Cl) 2 Fully stirring and heating to 110-130 ℃ for copolymerization.
The reaction formula of the step S1 in the preparation process is as follows:
the reaction formula of step S2 is:
compared with the prior art, the method has the beneficial effects that:
1) The invention provides a single-source ultrahigh-temperature ceramic precursor containing a Zr-C-Si main chain, which comprises a zirconocene structure, a flexible silicon chain segment and a Zr-C-Si main chain formed by combining C chains, and has the advantages and characteristics of no oxygen theoretically, good molecular chain flexibility, good solubility in toluene, a softening point of 140-185 ℃ and the like.
2) The invention provides a preparation method of a single-source ultrahigh-temperature ceramic precursor containing a Zr-C-Si main chain, which comprises the steps of firstly, preparing Cp 2 ZrCl 2 Reacting with Mg filings in a solvent to obtain Cp 2 Zr (II) equivalent active species are added, partial toluene/xylene is further added as a second-stage reaction solvent, the reaction temperature is increased, the kinetic influence of the reaction is reduced, and ClCH is added 2 Si(CH 3 ) 2 CH 2 Cl as Si source and active species Cp 2 And (3) carrying out copolymerization on Zr (II), and finally heating to 110-130 ℃ for polymerization to obtain the single-source ultrahigh-temperature ceramic precursor containing the Zr-C-Si main chain.
3) The preparation method has simple synthesis equipment and operation.
Drawings
In order to more clearly illustrate the technical problems of the present invention, the technical solutions in the embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is an optical photograph of a precursor of PZCS obtained in example 1 of the present invention;
FIG. 2 is an IR spectrum of a PZCS precursor obtained in example 1 of the present invention;
FIG. 3 is an XPS survey spectrum of a precursor of PZCS obtained in example 1 of the present invention;
FIG. 4 is a Gel Permeation Chromatography (GPC) spectrum of a PZCS precursor obtained in example 1 of the present invention.
Detailed Description
The technical problem underlying the present invention will be described in more detail below with reference to embodiments and drawings of embodiments, and it should be understood that the described embodiments are only some embodiments of the present invention. Based on the embodiments of the present invention, other embodiments obtained by persons skilled in the art without any creative work are within the protection scope of the present invention.
The solvents used in the present invention are all anhydrous solvents (water removal treatment), and the drugs used are all commercially available unless otherwise specified.
Example 1:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultrahigh temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg scrap.
S12: adding zirconocene dichloride and magnesium chips into THF according to the molar ratio of 1.
(2) Preparation of PZCS ceramic precursor
Vacuum concentration to remove Cp 2 About 1/3 THF solvent of Zr (II) active species solution, slowly dropping (CH) 3 ) 2 Si(CH 2 Cl) 2 Monomer (molar ratio Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) And uniformly stirring the mixture and a reaction solvent toluene at room temperature, heating to 110 ℃, reacting, keeping the temperature for 16h, naturally cooling to room temperature, filtering to remove magnesium salts, and performing vacuum concentration to obtain the orange PZCS ultrahigh-temperature ceramic precursor containing the Zr-C-Si main chain structure. The ceramic yield of the precursor at 900 ℃ is 43.985% (the precursor is heated to 900 ℃ under an inert atmosphere, the mass percentage of the final residual product, i.e. the 900 ℃ residual product/original product, is equal to the ceramic yield of the precursor at 900 ℃), and the softening point is 140-185 ℃.
The precursor obtained in this exampleThe morphology is shown in fig. 1, and the obtained precursor is powder. The infrared structure of the precursor is shown in FIG. 2, in which-CH is shown 3 Cp (C-H) and Si-CH 3 The presence of iso-structures indicates the chemical structure of the two monomers present in the PZCS precursor. From the XPS spectroscopy analysis of fig. 3, it follows that the precursor is composed mainly of C, si, cl, zr and O, where the presence of O may be the result of oxygen uptake during sample storage or transfer. Gel Permeation Chromatography (GPC) is an important method for measuring the molecular weight of a polymer, and as can be seen from FIG. 4, the number average molecular weight of the precursor obtained in this example is 848g/mol, and the weight average molecular weight is 1002g/mol, indicating that copolymerization occurs between the two monomers, resulting in a PZCS polymer precursor.
Example 2:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultrahigh-temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg scrap.
S12: adding zirconocene dichloride and magnesium chips into THF according to the molar ratio of 1.
(2) Preparation of PZCS ceramic precursor
Vacuum concentration to remove Cp 2 About 1/3 THF solvent of Zr (II) active species solution, slowly dropping (CH) 3 ) 2 Si(CH 2 Cl) 2 Monomer (Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) And uniformly stirring the mixture and a reaction solvent toluene at room temperature, heating to 110 ℃, reacting, keeping the temperature for 4 hours, naturally cooling to room temperature, filtering to remove magnesium salts, and performing vacuum concentration to obtain a yellow PZCS ultrahigh-temperature ceramic precursor containing a Zr-C-Si main chain structure.
This example is mainly for the purpose of studying the effect of reaction temperature on the performance of the precursor, and the results show that the ceramic yield of the obtained precursor at 900 ℃ is 45.077%, the softening point is more than 250 ℃, and the precursor has a high ceramic yield, but cannot be melted within 250 ℃.
Example 3:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultrahigh-temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg scrap.
S12: adding zirconocene dichloride and magnesium chips into THF according to the molar ratio of 1.
(2) Preparation of PZCS ceramic precursor
Vacuum concentration to remove Cp 2 About 1/3 THF solvent of Zr (II) active species solution, slowly add (CH) dropwise 3 ) 2 Si(CH 2 Cl) 2 Monomer (Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) And uniformly stirring the mixture and a reaction solvent toluene at room temperature, heating to 110 ℃, reacting, keeping the temperature for 8 hours, naturally cooling to room temperature, filtering to remove magnesium salts, and performing vacuum concentration to obtain a yellow PZCS ultrahigh-temperature ceramic precursor containing a Zr-C-Si main chain structure.
This example was conducted mainly for the purpose of examining the influence of the reaction temperature on the properties of the precursor, and the results showed that the ceramic yield of the obtained precursor was 45.783% at 900 ℃ and the softening point was > 250 ℃, but the precursor could not be melted at 250 ℃ although it had a high ceramic yield.
Example 4:
the embodiment provides a preparation method of a Zr-C-Si main chain single-source ultrahigh-temperature ceramic precursor, which comprises the following steps:
(1) Preparation of Cp 2 Zr (II) active species
S11: determination of Cp 2 ZrCl 2 Reaction molar ratio with Mg chips.
S12: adding zirconocene dichloride and magnesium chips into DMF (dimethyl formamide) according to the molar ratio of 1.
(2) Preparation of PZCS ceramic precursor
Slowly adding (CH) dropwise into the reaction flask by using a syringe 3 ) 2 Si(CH 2 Cl) 2 l monomer (molar ratio Cp) 2 Zr(Ⅱ)：(CH 3 ) 2 Si(CH 2 Cl) 2 =5: 4) After being uniformly stirred at room temperature, the mixture is heated to 120 ℃ for reaction and is kept for 16 hours, the mixture is naturally cooled to the room temperature, magnesium salts are removed through filtration, and vacuum concentration is carried out, so as to obtain the brown PZCS ultrahigh-temperature ceramic precursor containing the Zr-C-Si main chain structure.
This example is mainly to demonstrate the effect of different reaction solvents on the final precursor performance, and the results show that when the reaction solvent is changed to DMF, the ceramic yield of the obtained precursor at 900 ℃ is 35.235%, the softening point is 150-200 ℃, and the obtained precursor is fusible, but the ceramic yield is low.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (9)
1. The Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor is characterized by comprising the following molecular chain structures:
wherein the main chain structural unit is a Zr-C-Si chain, and n represents the degree of polymerization; the ultra-high temperature refers to the use temperature of the ceramics obtained by the Zr-C-Si main chain single-source ultra-high temperature ceramic precursor is above 1600 ℃; the softening point of the Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor is 140-185 ℃.
2. The method for preparing the single-source ultrahigh temperature ceramic precursor containing the Zr-C-Si main chain according to claim 1, characterized by comprising the following steps:
s1, preparation of Cp 2 Zr (ii) equivalent active species: cp is 2 ZrCl 2 Adding Mg chips into a first reaction solvent according to a predetermined molar ratio, fully stirring, reacting at room temperature-60 ℃ for 1-6 h, cooling to room temperature, filtering to remove excessive reactant magnesium chips, and obtaining black-purple Cp 2 Zr (II) equivalent active species solution;
s2, preparing a PZCS ceramic precursor: at Cp 2 Adding a certain proportion of (CH) into the Zr (II) solution 3 ) 2 Si(CH 2 Cl) 2 And a second reaction solvent, uniformly stirring at room temperature, heating to 110-130 ℃, reacting, keeping the temperature for 4-24 h, naturally cooling to room temperature, filtering to remove magnesium salts, and vacuum concentrating to obtain orange ultrahigh-temperature ceramic precursor powder containing a Zr-C-Si main chain structure.
3. The method for preparing a precursor of a Zr-C-Si backbone-containing single-source UHT ceramic as claimed in claim 2, wherein in step S1, cp 2 ZrCl 2 Molar ratio to Mg chips =1: (2-6).
4. The method for preparing a precursor of a ceramics with a Zr-C-Si backbone and a single source of superhigh temperature according to claim 2 or 3, characterized in that in step S1, cp 2 ZrCl 2 Molar ratio to Mg chips =1:6.
5. the method for preparing the single-source ultrahigh-temperature ceramic precursor containing the Zr-C-Si main chain according to claim 2, wherein in the step S1, the first reaction solvent is anhydrous THF or anhydrous DMF.
6. The method for preparing the Zr-C-Si backbone single-source ultrahigh temperature ceramic precursor as claimed in claim 2, wherein in step S2, said second reaction solvent is one of toluene, xylene and anhydrous DMF.
7. The method for preparing a precursor of a Zr-C-Si backbone-containing single-source UHT ceramic as claimed in claim 2, wherein in step S2, cp 2 Zr (II) active species with (CH) 3 ) 2 Si(CH 2 Cl) 2 The molar ratio of the monomers is 5 (4-6).
8. The method for preparing a precursor of a ceramics with a Zr-C-Si backbone monosource at ultra high temperature according to claim 2 or 7, wherein in step S2, cp 2 Zr (II) active species with (CH) 3 ) 2 Si(CH 2 Cl) 2 The molar ratio of the monomers is 5.
9. The method for preparing the Zr-C-Si main chain-containing single-source ultrahigh-temperature ceramic precursor as claimed in claim 2, wherein the second solvent is added in one of the following manners:
a. when the second reaction solvent and the first reaction solvent are the same substance, a certain proportion of (CH) is directly dripped 3 ) 2 Si(CH 2 Cl) 2 Fully stirring the monomers, and heating to 110-130 ℃ for copolymerization;
b. when the second reaction solvent is different from the first reaction solvent, cp is 2 Putting the Zr (II) active species solution into a three-neck flask, and carrying out vacuum concentration at room temperature to remove a first reaction solvent not less than 1/3; using dropping funnel to the remaining Cp 2 Injecting a second reaction solvent into the Zr (II) active species solution, and stirring to ensure that Cp is 2 Zr (II) active species are evenly dispersed in the mixed solvent, and then a reaction monomer (CH) is slowly dropped into the solution by utilizing a disposable injector 3 ) 2 Si(CH 2 Cl) 2 Fully stirring for 30min and heating to 110-130 ℃ for copolymerization.
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