CN115216016A - Solid polysilazane and preparation method and application thereof - Google Patents

Solid polysilazane and preparation method and application thereof Download PDF

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CN115216016A
CN115216016A CN202110431496.8A CN202110431496A CN115216016A CN 115216016 A CN115216016 A CN 115216016A CN 202110431496 A CN202110431496 A CN 202110431496A CN 115216016 A CN115216016 A CN 115216016A
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substituted
unsubstituted
polysilazane
dichlorosilane
aryl
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CN115216016B (en
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罗永明
徐彩虹
刘丹
陈艳杰
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Institute of Chemistry CAS
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms

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Abstract

The invention discloses a preparation method of solid polysilazane, which comprises the following steps: (1) The raw materials comprise dichlorosilane and trichlorosilane, and silazane oligomer is prepared under the protection of inert gas; the dichlorosilane and the trichlorosilane do not contain Si-H bonds; (2) And (2) introducing inert gas flow into the silazane oligomer prepared in the step (1), and reacting at the heating temperature of not higher than 300 ℃ to prepare solid polysilazane. In the invention, dichlorosilane and trichlorosilane which do not contain Si-H bonds are used for ammonolysis reaction to prepare silazane polymer, the silazane polymer is treated at a certain temperature to obtain soluble solid polysilazane, and the reaction uses thermal polymerization without using a catalyst, so that the influence of the catalyst on the performance of the subsequently prepared ceramic material is avoided.

Description

Solid polysilazane and preparation method and application thereof
Technical Field
The invention relates to solid polysilazane and a simple and efficient preparation method and application thereof, belonging to the field of polymer synthesis.
Background
Polysilazane is an element organic polymer whose main chain is mainly Si-N bond and side chain contains organic group or hydrogen, and can be converted into silicon nitride-based ceramic with excellent temperature resistance and good oxidation resistance under a certain condition. The soluble and meltable solid polysilazane not only has the application of liquid polysilazane, such as being used for preparing ceramic matrix composite materials, high-temperature-resistant adhesives, coatings, films and the like, but also can be used for preparing ceramic fibers, hot-melt coatings, prepregs suitable for dry hot-melt molding and the like.
EP0255132 uses a reaction product of diorganodichlorosilane, methylhydrodichlorosilane and hexamethyldisilazane to be treated at a high temperature of 350-450 ℃ to obtain solid polycarbosilazane for preparing SiCN fiber by melt spinning; patent CN 104817701A discloses a method for preparing thermoplastic polysilazane by taking methylhydrogen dichlorosilane and methyl vinyl dichlorosilane as raw materials, taking n-hexane as a solvent to carry out ammonolysis reaction, and carrying out thermal polymerization under the action of a catalyst. Naslain (j. Mater. Sci.,28, 3059-3068, 1993) utilizes dimethyldichlorosilane and 1, 3-dichloro-1, 3-dimethyldisilazane to condense under the action of sodium metal to form polysilazane, which is treated at high temperatures of 335-372 ℃ to form solid polycarbosilazane for melt spinning. Motz, (Ceramic Materials and Components for engineering ", wiley-VCH Verlag GmbH & Co. KGaA (2001) pp.581-585) first hydrosilylation reacted with methylhydrodichlorosilane and methylvinyldichlorosilane, and the addition product was then aminolyzed to give low molecular weight solid polycarbosilazane (ABSE) which had low Ceramic yield due to the absence of reactive groups. Seyforth (Journal of the American Ceramic Society,1984,67 (7): 132-133) uses methylhydrodichlorosilane as a reaction raw material, tetrahydrofuran as a reaction solvent, and alkali metal as a catalyst, and performs ammonolysis reaction at 0 ℃ and polymerizes under the action of the alkali metal catalyst to obtain melt-spinnable polysilazane containing four-membered rings and six-membered rings. Patent CN 111303433A discloses polysilazane with excellent spinning performance and its preparation and melt spinning, wherein methyl hydrogen dichlorosilane and dimethyl dichlorosilane are subjected to ammonolysis reaction to obtain silazane oligomer, the oligomer is subjected to stepwise thermal polymerization, and solid polysilazane can be obtained at the maximum treatment temperature of 330 ℃ for spinning. At present, the catalyst is used for preparing fusible and soluble solid polysilazane, or needs to be processed at higher temperature, or needs to be polymerized under the action of the catalyst to obtain the solid polysilazane, so that the polymerization cost and the complexity of the preparation process are greatly increased, and in addition, when the catalytic polymerization process is adopted, the catalyst generally remains in the polysilazane, thereby influencing the performance of SiCN ceramic formed by converting the polysilazane.
Disclosure of Invention
In order to solve the technical problems, the invention provides a simple method, and soluble and meltable solid polysilazane can be prepared by adopting lower temperature.
The technical scheme of the invention is as follows:
a method of preparing a solid polysilazane, the method comprising the steps of:
(1) The raw materials comprise dichlorosilane and trichlorosilane, and silazane oligomer is prepared under the protection of inert gas; the dichlorosilane and the trichlorosilane do not contain Si-H bonds;
(2) And (2) introducing inert gas flow into the silazane oligomer prepared in the step (1), and reacting at the heating temperature of not higher than 300 ℃ to prepare solid polysilazane.
According to the invention, the starting material of step (1) does not contain chlorosilanes containing Si-H bonds.
According to the present invention, in step (1), the dichlorosilane refers to a commercially available dichlorosilane containing no Si-H bond, and for example, has a structural formula shown in formula 1:
(R 1 )(R 2 )SiCl 2 (formula 1)
In the formula 1, R 1 And R 2 Identical or different, independently of one another, from substituted or unsubstituted hydrocarbon radicals, the substituents being selected from alkyl, alkenyl, alkynyl or aryl radicals.
Illustratively, said R 1 And R 2 The substituents are the same or different and are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl and substituted or unsubstituted aryl, and the substituents are selected from alkyl or aryl.
In step (1), the trichlorosilane is commercially available trichlorosilane containing no Si-H bond, and has a structural formula shown in formula 2:
R 3 SiCl 3 (formula 2)
In the formula 2, R 3 Is selected from substituted or unsubstituted hydrocarbyl, and the substituent is selected from alkyl, alkenyl, alkynyl or aryl.
Illustratively, said R 3 The aryl group is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl and substituted or unsubstituted aryl, and the substituent is selected from alkyl or aryl.
Illustratively, the substituted or unsubstituted alkyl is selected from substituted or unsubstituted C 1-6 Alkyl groups, for example selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl or 1, 2-dimethylbutyl groups and the like or isomers thereof, the substituents being aryl groups (e.g. phenyl groups).
Illustratively, the substituted or unsubstituted alkenyl group is selected from substituted or unsubstituted C 2-6 Alkenyl, for example from vinyl, allyl, (E) -2-methylvinyl, (Z) -2-methylvinyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (Z) -pent-2-enyl, (E) -pent-1-enyl, (Z) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E) -hex-1-enyl, (Z) -hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E) -1-methylprop-1-enyl, (Z) -1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -1-methylbut-2-enyl, (Z) -1-methylbut-2-enyl, (E) -3-methylbut-1-enyl, (Z) -3-methylbut-2-enylThe group but-1-enyl, (E) -2-methylbut-1-enyl, (Z) -2-methylbut-1-enyl, (E) -1-methylbut-1-enyl, (Z) -1-methylbut-1-enyl, 1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl and the like, and the substituent is an aryl group (e.g., phenyl).
Illustratively, the substituted or unsubstituted alkynyl group is selected from substituted or unsubstituted C 2-6 <xnotran> , , -1- , -2- , -1- , -2- , -3- , -1- , -2- , -3- , -4- , -1- , -2- , -3- , -4- , -5- ,1- -2- ,2- -3- ,1- -3- ,1- -2- ,3- -1- ,1- -2- ,3- -4- ,2- -4- ,1- -4- ,2- -3- ,1- -3- , 4- -2- ,1- -2- , 4- -1- ,3- -1- ,2- -3- ,1- -3- ,1- -2- ,1- -2- ,1- -2- ,2,2- -3- , </xnotran> 1, 1-dimethylbut-3-ynyl, 1-dimethylbut-2-ynyl or 3, 3-dimethylbut-1-ynyl; in particular, said alkynyl group is selected from ethynyl, prop-1-ynyl or prop-2-ynyl; the substituent is an aryl group (e.g., phenyl).
Illustratively, the substituted or unsubstituted aryl is selected from substituted or unsubstituted C 6-20 Aryl, for example selected from: having 6 carbon atoms in the ring (' C) 6 Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C 9 Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C 13 Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C) 14 Aryl), such as anthracyl). When said C is 6-20 When the aryl group is substituted, it may be mono-or polysubstituted. The substituent is alkyl (such as methyl, ethyl, etc.), arylA radical (e.g. phenyl). And, the substitution site thereof is not limited, and may be, for example, ortho-, para-or meta-substitution.
Illustratively, said R 1 And R 2 Identical or different, independently of one another, from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isopentyl, ethenyl, propenyl, styryl, phenyl, benzyl, naphthyl, 4-methylphenyl and the like.
Illustratively, the dichlorosilane includes, but is not limited to, at least one of methylvinyldichlorosilane, methylpropenyldichlorosilane, methylstyryldichlorosilane, ethylvinyldichlorosilane, divinyldichlorosilane, p-vinyldichlorosilane, phenylvinyldichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, di-n-butyldichlorosilane, diisopentyldichlorosilane, dipropenyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, methylphenyldichlorosilane, dibenzyldichlorosilane, diisobutyldichlorosilane, p-tolyldichlorosilane, and the like.
Illustratively, said R 3 At least one selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isopentyl, ethenyl, propenyl, styryl, phenyl, benzyl, naphthyl, 4-methylphenyl and the like.
Illustratively, the trichlorosilane includes, but is not limited to, at least one of methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, propyltrichlorosilane, isopropyltrichlorosilane, butyltrichlorosilane, and the like.
According to the invention, in step (1), the molar ratio of dichlorosilane to trichlorosilane in the raw materials is 1 to 1, and can be, for example, 1.
According to the invention, in the step (1), the raw materials also comprise ammonia gas, and when the pH value of the system is 9-10, the ammonia gas is stopped to be added.
According to the invention, in step (1), the raw material further comprises a chloride containing a hetero element. Illustratively, the hetero-element includes, but is not limited to, at least one of Al, B, ti, zr, hf, and the like.
Illustratively, the molar ratio of the chloride containing the hetero element to the dichlorosilane is (0.01-2): 1, such as (0.05-1): 1, and such as (0.1-0.5): 1.
According to the invention, in the step (1), the silazane oligomer is prepared by a method which comprises the following steps: under the protection of inert gas, dichlorosilane and trichlorosilane are dissolved in a solvent according to the proportion and are mixed evenly, and NH is introduced 3 Heating for reaction until the pH value of the system is 9-10, and stopping introducing NH 3 And preparing silazane oligomer.
According to the invention, in the step (1), the silazane oligomer is prepared by a method which comprises the following steps: under the protection of inert gas, dichlorosilane, trichlorosilane and chloride containing miscellaneous elements are dissolved in solvent according to the proportion, mixed evenly, and NH is introduced 3 Heating for reaction until the pH value of the system is 9-10, and stopping introducing NH 3 And preparing silazane oligomer containing hetero element.
In the step (1), the solvent includes, but is not limited to, C5 to C10 alkanes, ethers, tetrahydrofuran, aromatics, acetone, etc., and the C5 to C10 alkanes may be, for example, pentane, n-hexane, heptane, octane, nonane, decane, etc.; the ethers include, but are not limited to, petroleum ether; the aromatic compound may be, for example, benzene, toluene, xylene.
In the step (1), the volume ratio of the sum of the volumes of the dichlorosilane and the trichlorosilane to the solvent is 1.
In the step (1), the preparation method of the silazane oligomer comprises the following specific steps: under the protection of inert atmosphere, adding solvent, dichlorosilane and trichlorosilane in proportion into a three-neck flask provided with a stirrer, an air inlet pipe and an air outlet pipe, mixing uniformly, and then introducing NH 3 Heating for reaction until the pH value of the system is between 9 and 10, stopping introducing ammonia, and filtering a byproduct NH of the ammonolysis reaction after the reaction is finished 4 And Cl, collecting the filtrate, and carrying out vacuum concentration at 20-100 ℃ under 10-500 Pa to remove the solvent, thereby obtaining the silazane oligomer.
In the step (1), the preparation method of the silazane oligomer containing the hetero element specifically comprises the following steps: under the protection of inert atmosphere, adding solvent, dichlorosilane, trichlorosilane and chloride containing miscellaneous elements into a three-mouth bottle provided with a stirrer, an air inlet pipe and an air outlet pipe according to a proportion, uniformly mixing, and then introducing NH 3 Heating for reaction until the pH value of the system is between 9 and 10, stopping introducing ammonia, and filtering a byproduct NH of the ammonolysis reaction after the reaction is finished 4 And Cl, collecting the filtrate, and performing vacuum concentration at 20-100 ℃ and 10-500 Pa to remove the solvent to obtain the silazane oligomer.
In the step (1), the inert gas comprises nitrogen or argon; but are not limited to, nitrogen or argon.
In the step (1), the temperature of the heating reaction is-20 to 20 ℃. For example, the temperature may be-20 ℃, 10 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 18 ℃ and 20 ℃.
In the step (2), the flow rate of the inert gas ranges from 10ml/min to 500ml/min. For example, 10ml/min, 50ml/min, 100ml/min, 200ml/min, 300ml/min, 400ml/min, 450ml/min, 500ml/min may be mentioned.
In step (2), the heating temperature is in the range of 150 to 290 ℃, for example 160 to 270 ℃, further for example 160 to 250 ℃, and illustratively 150, 160, 170, 180, 200, 210, 220, 230, 240, 250 ℃.
In the step (2), the reaction is carried out in vacuum with the vacuum degree of 200-10 5 Pa。
In the step (2), the reaction time is 0.5 to 10 hours, preferably 1 to 5 hours.
In the step (2), the inert gas comprises nitrogen or argon; but are not limited to, nitrogen or argon.
The invention also provides a solid polysilazane which is fusible and soluble.
In the present invention, the solid polysilazane is meltable, which means that its softening point is not higher than 200 ℃.
In the present invention, the solid polysilazane is soluble means that it can be dissolved in at least one of the following organic solvents: an aromatic organic solvent, an ester organic solvent, a ketone organic solvent or a furan organic solvent; for example, it can be dissolved in an organic solvent such as tetrahydrofuran, acetone, toluene, xylene, or butyl acetate.
According to the invention, the solid polysilazane has a number-average molecular weight of 500 to 15000 and a softening point of 50 to 160 ℃. Illustratively, the softening point is 50, 60, 62, 65, 70, 75, 78, 80, 100, 110, 120, 130, 140, 150, or 160 ℃.
According to the present invention, the solid polysilazane may further comprise a hetero-element including, but not limited to, at least one of Al, B, ti, zr, hf, etc.
According to the invention, the solid polysilazane is prepared by the above method.
The invention also provides application of the solid polysilazane to preparation of ceramic fibers, prepregs, hot-melt coatings and the like.
Advantageous effects
Firstly, dichlorosilane and trichlorosilane which do not contain Si-H bonds are used for ammonolysis reaction to prepare silazane polymer, the silazane polymer is treated at a certain temperature to obtain fusible and soluble solid polysilazane, thermal polymerization is used for reaction, a catalyst is not used, and the influence of the catalyst on the performance of a subsequently prepared ceramic material is avoided.
Secondly, the post-polymerization temperature of the invention is lower than 300 ℃ (for example, 160 ℃ to 270 ℃), which is much lower than the polymerization temperature reported in the literature, thus reducing the requirements on the performance of the reaction device and saving energy.
Thirdly, the chlorosilane raw material adopted by the invention does not contain Si-H bonds, and the degree of a branched structure in the product is controlled by lower post-polymerization temperature (lower than 300 ℃, for example, 160-270 ℃), so that the fusible soluble solid polysilazane is synthesized.
Fourth, the present invention is useful not only for preparing polysilazanes, but also for preparing fusible and soluble polysilazanes containing miscellaneous elements including, but not limited to, al, B, ti, zr, hf.
Fifthly, the soluble and meltable solid polysilazane prepared by the method can also be used for preparing ceramic fibers, prepregs and hot melt coatings.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
A method of preparing a solid polysilazane, the method comprising the steps of:
s1: preparation of silazane oligomer: under the protection of inert atmosphere, 500ml of dried toluene solvent, 0.5 mol of dimethyldichlorosilane and 0.5 mol of methyltrichlorosilane are added into a 1L bottle provided with a stirrer, an air inlet pipe and an air outlet pipe, the mixture is uniformly stirred, and then dried NH is introduced at the speed of 100ml/min 3 Stirring at 5 ℃ to carry out ammonolysis reaction; stopping introducing ammonia until the pH value of the system reaches 9, and filtering a byproduct NH of the ammonolysis reaction after the reaction is finished 4 And Cl, and collecting the toluene filtrate.
S2: vacuum concentrating the toluene filtrate at 70 ℃ and 10Pa to remove toluene, thus obtaining silazane oligomer;
s3: under the protection of inert gas, 50 g of silazane oligomer prepared in S2 is added into a 200ml three-neck flask; nitrogen gas was introduced at 50ml/min, and then the temperature of the reaction flask was raised to 220 ℃ to heat-treat for 2 hours, to prepare colorless or pale yellow solid polysilazane under normal pressure. The solid polysilazane has a softening point of 78 ℃ and a number average molecular weight of 1100. The solid polysilazane may be dissolved in tetrahydrofuran, acetone, toluene, xylene, butyl acetate.
Example 2
Example 2 differs from example 1 in that: the heat treatment temperature in the step S3 in example (1) was raised to 250 ℃ for 5 hours to give a pale yellow cured polysilazane having a softening point of 160 ℃ and a number average molecular weight of 1150. The solid polysilazane may be dissolved in tetrahydrofuran, acetone, toluene, xylene, butyl acetate.
Example 3
A method of preparing a solid polysilazane, the method comprising the steps of:
s1: preparation of silazane oligomer: under the protection of inert atmosphere, 1500ml of dried petroleum ether (60-90 ℃) solvent, 2 mol of dimethyldichlorosilane and 4 mol of vinyl trichlorosilane are added into a 3L bottle provided with a stirrer, an air inlet pipe and an air outlet pipe, the mixture is uniformly stirred, and then dried NH is introduced at the speed of 500ml/min 3 Stirring at-20 ℃ for ammonolysis reaction; stopping introducing ammonia until the pH value of the system reaches 10, and filtering a byproduct NH of the ammonolysis reaction after the reaction is finished 4 And Cl, and collecting petroleum ether filtrate.
S2: vacuum concentrating the petroleum ether filtrate at 20 deg.C and 500Pa to remove petroleum ether to obtain silazane oligomer;
s3: 100 g of silazane oligomer prepared in S2 was charged into a 250ml three-neck flask under an inert gas atmosphere; nitrogen gas is introduced at the rate of 10ml/min, and then the temperature of the reaction bottle is raised to 160 ℃ and the heat treatment is carried out for 3 hours under the condition of 200Pa, thus obtaining pale yellow solid polysilazane. The solid polysilazane has a softening point of 62 ℃ and a number average molecular weight of 1080. The solid polysilazane may be dissolved in tetrahydrofuran, acetone, toluene, xylene, butyl acetate.
Example 4
A method of preparing a solid polysilazane, the method comprising the steps of:
s1: preparation of silazane oligomer: under the protection of inert atmosphere, 600ml of dried tetrahydrofuran solvent, 0.4 mol of methyl vinyl dichlorosilane and 0.4 mol of phenyl trichlorosilane are added into a 1L bottle provided with a stirrer, an air inlet pipe and an air outlet pipe, the mixture is uniformly stirred, and then dried NH is introduced at the speed of 10ml/min 3 Stirring the mixture at the temperature of 20 ℃ to carry out ammonolysis reaction; stopping the reaction until the pH value of the system reaches 9.5Ammonia, filtering by-product NH of ammonolysis reaction after reaction 4 And Cl, and collecting tetrahydrofuran filtrate.
S2: concentrating tetrahydrofuran filtrate at 50 deg.C under 200Pa, and removing petroleum ether to obtain silazane oligomer;
s3: under the protection of inert gas, 30 g of silazane oligomer prepared in S2 is added into a 100ml three-neck flask; after introducing nitrogen gas at a flow rate of 20ml/min, the temperature of the reaction flask was raised to 210 ℃ and heat-treated under vacuum at 1000Pa for 4 hours to obtain colorless solid polysilazane. The solid polysilazane has a softening point of 140 ℃ and a number average molecular weight of 1080. The solid polysilazane may be dissolved in tetrahydrofuran, acetone, toluene, xylene, butyl acetate.
Example 5
A method for preparing zirconium-containing solid polysilazane, comprising the steps of:
s1: preparation of silazane oligomer: under the protection of inert atmosphere, 500ml of dried toluene solvent, 0.5 mol of dimethyldichlorosilane, 0.5 mol of methyltrichlorosilane and 0.05 mol of zirconium tetrachloride are added into a 1L bottle provided with a stirrer, an air inlet pipe and an air outlet pipe, the mixture is uniformly stirred, and then dried NH is introduced at the speed of 100ml/min 3 Stirring at 5 ℃ to carry out ammonolysis reaction; stopping introducing ammonia until the pH value of the system reaches 9, and filtering a byproduct NH of the ammonolysis reaction after the reaction is finished 4 And Cl, and collecting the toluene filtrate.
S2: vacuum concentrating the toluene filtrate at 70 deg.C and 10Pa to remove toluene to obtain zirconium-containing silazane oligomer;
s3: under the protection of inert gas, 50 g of zirconium-containing silazane oligomer prepared in the step S2 is added into a 200ml three-neck flask; nitrogen gas is introduced at the flow rate of 50ml/min, then the temperature of the reaction bottle is raised to 150 ℃, and the reaction bottle is heated under vacuum of 200Pa for 2 hours, so that yellow solid zirconium-containing polysilazane is prepared under normal pressure. The solid zirconium-containing polysilazane has a softening point of 78 ℃ and a number average molecular weight of 1100. The solid zirconium-containing polysilazane may be dissolved in tetrahydrofuran, acetone, toluene, xylene, butyl acetate.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method of preparing a solid polysilazane, comprising the steps of:
(1) The raw materials comprise dichlorosilane and trichlorosilane, and silazane oligomer is prepared under the protection of inert gas; the dichlorosilane and the trichlorosilane do not contain Si-H bonds;
(2) And (2) introducing inert gas flow into the silazane oligomer prepared in the step (1), and reacting at the heating temperature of not higher than 300 ℃ to prepare solid polysilazane.
2. The method of claim 1, wherein in step (1), the dichlorosilane has the formula shown in formula 1:
(R 1 )(R 2 )SiCl 2 (formula 1)
In the formula 1, R 1 And R 2 Identical or different, independently of one another, from substituted or unsubstituted hydrocarbon radicals, the substituents being selected from alkyl, alkenyl, alkynyl or aryl radicals.
Preferably, said R is 1 And R 2 The substituents are the same or different and are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl and substituted or unsubstituted aryl, and the substituents are selected from alkyl or aryl.
3. The method according to any one of claims 1-2, wherein in step (1), the trichlorosilane has a structural formula shown in formula 2:
R 3 SiCl 3 (formula 2)
In the formula 2, R 3 Is selected from substituted or unsubstituted hydrocarbyl, and the substituent is selected from alkyl, alkenyl, alkynyl or aryl.
PreferablySaid R is 3 The aryl group is selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl and substituted or unsubstituted aryl, and the substituent is selected from alkyl or aryl.
4. The method of any one of claims 1-3, wherein the substituted or unsubstituted alkyl group is selected from substituted or unsubstituted C 1-6 An alkyl group;
the substituted or unsubstituted alkenyl is selected from substituted or unsubstituted C 2-6 An alkenyl group;
the substituted or unsubstituted alkynyl is selected from substituted or unsubstituted C 2-6 An alkynyl group;
the substituted or unsubstituted aryl group is selected from substituted or unsubstituted C 6-20 An aryl group;
the substituent is aryl.
5. The method according to any one of claims 1 to 4, wherein in the step (1), the molar ratio of dichlorosilane to trichlorosilane in the raw material is 1 to 1;
preferably, in the step (1), ammonia gas is further included in the raw materials, and the ammonia gas is stopped from being added when the pH of the system is 9-10.
6. The process according to any one of claims 1 to 5, wherein in step (1), the raw material further comprises a chloride containing a hetero element; the hetero element includes but is not limited to at least one of Al, B, ti, zr and Hf.
Preferably, the molar ratio of the chloride containing the hetero element to the dichlorosilane is (0.01-2): 1.
7. The process according to any one of claims 1 to 6, wherein in step (1), the ratio of the sum of the volumes of dichlorosilane and trichlorosilane to the volume of the solvent is from 1.
8. A solid polysilazane, wherein said solid polysilazane is fusible; the solid polysilazane is meltable, namely the softening point of the solid polysilazane is not higher than 200 ℃; the solid polysilazane is soluble means that it can be dissolved in at least one of the following organic solvents: aromatic organic solvents, ester organic solvents, ketone organic solvents or furan organic solvents.
Preferably, the solid polysilazane is prepared by the process of any one of claims 1-7.
9. The solid polysilazane of claim 8, wherein the solid polysilazane has a number average molecular weight of 500 to 15000.
Preferably, the solid polysilazane further comprises a hetero element including, but not limited to, at least one of Al, B, ti, zr, hf.
10. Use of a solid polysilazane according to any one of claims 8-9, for the production of ceramic fibers, prepregs or hot-melt coatings.
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