CN112266482B - Polyaluminocarbosilane and preparation method thereof - Google Patents
Polyaluminocarbosilane and preparation method thereof Download PDFInfo
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Abstract
The invention provides polyaluminium carbosilane and a preparation method thereof, and the method takes silane containing a silicon-hydrogen bond as a first raw material and carries out hydrosilylation reaction with a second raw material containing (X) nSi (Y) m to obtain a first intermediate product; and finally, replacing the first raw material with the third intermediate product, sequentially carrying out hydrosilylation, reduction reaction and solid-liquid separation to prepare polycarbosilane with high silicon hydrogen content, and reacting the polycarbosilane with high silicon hydrogen content with an aluminum-containing compound to obtain the polyaluminum carbosilane. The polyaluminium carbosilane prepared by the method has high content of silicon-hydrogen bonds and high content of aluminum elements, and the content of the silicon-hydrogen bonds and the content of the aluminum elements can be regulated and controlled.
Description
Technical Field
The invention belongs to the field of silicon carbide ceramics, and particularly relates to polyaluminocarbosilane and a preparation method thereof.
Background
Polyaluminocarbosilane has been noted by researchers at home and abroad as a precursor of the third generation silicon carbide fiber, and has been mass-produced as a precursor of the third generation silicon carbide fiber. The introduction of aluminum can inhibit the crystallization of silicon carbide under high temperature conditions, and is the key to the successful preparation of the aluminum-containing third-generation silicon carbide fiber.
However, the synthesis route of poly-aluminum-carbon-silane is single, and the poly-aluminum-carbon-silane is prepared by the reaction of a silicon-hydrogen bond in a product obtained by pyrolysis of poly-dimethyl-silane and an aluminum-containing compound: the disadvantages of the polydimethyl silane can not be escaped no matter the normal pressure reaction, the high pressure reaction, the polysilane as the reaction raw material or the low molecular weight polycarbosilane as the reaction raw material: the active groups are only one, the content of the silicon hydrogen is too low, the silicon hydrogen bond content in polycarbosilane synthesized by polydimethylsiloxane is 0.7-0.8% by a chemical method, the theoretical content of the silicon hydrogen bond is 1.72%, and the actually measured value is far lower than the theoretical value (Songli, Friekun. SiC precursor-application research development of polycarbosilane [ J ] Chinese material development, 2013, 032(004):243 one-wall 248.). The synthesis of polyaluminocarbosilane (cf. Yuan-Naiyi, Songyong-Yong. Si (Al) C fiber precursor polyaluminocarbosilane [ J ] Proc. national defense science and technology, 2017,039(001): 182-: silicon hydrogen bond is broken, silicon is connected to a heterogeneous element, hydrogen is connected to a ligand of a compound of the heterogeneous element, the reaction consumes silicon hydrogen bonds, the content of the silicon hydrogen bonds in the polycarbosilane is not high, and after aluminum element is introduced by consuming the silicon hydrogen bonds, the content of the silicon hydrogen bonds in a product is lower, so that the reaction activity of the polyaluminocarbosilane is low, and a plurality of problems in the application process of the polyaluminocarbosilane are caused, such as low reaction activity caused by air not melting, and auxiliary operation is required, for example, the synthesis of the polyaluminocarbosilane as a precursor of a thermal crosslinking (Yuanchi, Song Yongcai. Si (Al) C fiber precursor [ J ]. national defense science and technology university report, 2017,39(001):182-188.) is adopted to solve the problem of the Polyaluminocarbosilane (PACS) in the air not melting process: the PACS fibers were not melted until 240 ℃ and Polycarbosilane (PCS) fibers were completed at 200 ℃. PACS itself contains lower relative Si-H content than PCS, and its reaction rate below 190 deg.C is much lower than PCS. The reaction rate increases gradually when the temperature is >190 ℃ and the temperature at which the gel appears is also higher than for PCS fibers, requiring 200 ℃. The lower active group content and the greater steric hindrance resulting from the high molecular weight make PACS fibers difficult to achieve without melting at lower temperatures. To further increase the degree of crosslinking, the non-melting temperature must therefore be increased, but at the same time more oxygen is introduced.
Further problems have been troubling the application of polyaluminocarbosilanes, for example, when the polyaluminocarbosilanes are used as ceramic binders, the silicon-hydrogen content is further reduced when the aluminum element compounds are fed at a high proportion, the polyaluminocarbosilanes have lower reactivity, and a large amount of ligands of the aluminum element are found to remain, so that the production yield of the product ceramic is reduced, the properties are unstable, the spinning performance is poor and the like, so that the polyaluminocarbosilanes with high aluminum element content are difficult to prepare and apply (Yuan, Song Yong.
In conclusion, the existing polyaluminum carbosilane has low silicon hydrogen content, and polyaluminum carbosilane with high aluminum element content and certain silicon hydrogen reaction activity are difficult to prepare.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of polyaluminum carbosilane, which comprises the following steps:
step 1, carrying out hydrosilylation reaction on a first raw material and a second raw material at a mass ratio of 1: 0.1-3.2 at 20-200 ℃ for 1-30 h to prepare a first intermediate product;
step 2, adding a reducing agent into the first intermediate product, and reacting for 2-20 hours at-20-120 ℃ to obtain a second intermediate product;
step 3, carrying out solid-liquid separation treatment on the second intermediate product, and removing solids after solid-liquid separation to obtain a third intermediate product;
step 4, replacing the first raw material in the step 1 with the third intermediate product, and sequentially repeating the step 1, the step 2 and the step 3 to obtain polycarbosilane with high silicon-hydrogen content;
step 5, mixing the polycarbosilane with high silicon-hydrogen content prepared in the step 4 and an aluminum-containing compound according to the mass ratio of 1: 0.01-8, reacting for 0.5-50 h at 60-360 ℃ to obtain the polyaluminum carbosilane;
wherein the first raw material is silane containing Si-H; the second raw material contains (X) nSi (Y) m; x is CH2Is CH-A-or CH2Wherein A is at least one of acyl, acyloxy, saturated alkane, phenyl and cyclic hydrocarbonOne kind of the material is selected; y is at least one of Cl, Br, I and alkoxy, the sum of n and m is equal to 3 or 4, n is one of 1 or 2, and m is 2 or 3.
In step 1, a solvent is added during the hydrosilylation reaction of the first raw material and the second raw material, and the mass ratio of the first raw material to the solvent is 1: 0-3.5.
Further, the solvent is at least one of xylene, toluene and cyclohexane.
Further, when the solvent is 0, the first raw material is liquid silane containing a silicon-hydrogen bond. When the solvent is not 0, the first raw material is solid silane containing a silicon-hydrogen bond, and certainly can be liquid silane.
In step 1, the first raw material may be polycarbosilane and/or polysilane containing silicon-hydrogen bonds, or polyaluminocarbosilane with a low aluminum content.
Further, the polysilane is LPS (polysilane, polydimethylsilane pyrolysis, silicon-hydrogen bond of 0.4 mol-0.5 mol/100 g).
Further, the polycarbosilane is LPCS (liquid polycarbosilane, polydimethysilane pyrolysis, silicon hydrogen bond of 0.6-0.7 mol/100g) and PCS (solid polycarbosilane, polydimethysilane pyrolysis, silicon hydrogen bond of 0.5-0.6 mol/100 g).
Furthermore, the softening point of the polyaluminum carbosilane with low aluminum content is 200-210 ℃, the Alwt% is 0.6%, and the silicon-hydrogen bond is 0.45mol/100g, and the synthesis method refers to Yuanyin, Songyong, Si (Al) C fiber precursor polyaluminum carbosilane synthesis [ J ] reported by national defense science and technology university, 2017,039(001): 182-.
Further, in step 1, the second starting material may be selected from one or more of the following compounds: vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri-n-propoxysilane, vinyltriisopropoxysilane, vinyltri-n-butoxysilane, vinyltriisobutoxysilane, vinyltri-t-butoxysilane, methylvinyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldi-n-propoxysilane, methylvinylmono-n-propoxysilane, methylvinyldiisopropoxysilane, phenylvinyldiethoxysilane, phenylvinyldimethoxysilane, phenylvinyldi-n-propoxysilane, vinylmonomethoxy-n-propoxysilane, vinyldimethoxymono-n-butoxysilane; vinyltrichlorosilane, vinyltriiodosilane, vinyltribromosilane, vinyldichloromonomethoxysilane, vinyldichloroethoxysilane, vinyldichloron-propoxysilane, vinyldichloroisopropoxysilane, vinyldichloron-butoxysilane, vinyldichloroisobutoxysilane, vinylmonochlorodimethoxysilane, vinylmonochlorodiethoxysilane, methylvinylmonochlorodiethoxysilane, methylvinylmonochloropropoxysilane, methylvinylmonochlorodiethoxysilane, methylvinylmonochloropropoxoxysilane, methylvinylmonochlorodiethoxysilane, vinylmonochlorodiethoxysilane, vinyldichloroethoxysilane, vinylmonochlorodiethoxysilane, vinyldichloroethoxysilane, vinylethoxysilane, vinyldichloroethoxysilane, vinylethoxysilane, vinylethoxy, Vinyl monochlorodin-propoxysilane, vinyl monochlorodiiso-propoxysilane, propenyl trichlorosilane, propenyl tribromosilane, propenyl triiodosilane, propenyl triethoxysilane, propenyl trimethoxysilane, propenyl tripropoxysilane, methacryl diethoxysilane, methacryl dimethoxysilane, methacryl dipropoxysilane, phenylpropyl diethoxysilane, phenylpropenyl dimethoxysilane, phenylpropenyl dipropoxysilane, propenyl monomethoxy-monopropoxysilane; monovinyl-propenyl diethoxysilane, monovinyl-propenyl dimethoxysilane, monovinyl-propenyl dipropoxysilane, divinyldiethoxysilane, divinyldimethoxysilane, divinyldi-n-propoxysilane, divinyldiisopropoxysilane, divinyl di-n-butoxysilane, divinyl dichlorosilane, divinyl diiodosilane, divinyl dibromosilane, divinyl monochloromethoxysilane, divinyl monochloroethoxysilane, divinyl monochloro-n-propoxysilane, divinyl monochloro-isopropoxysilane, divinyl monochloro-n-butoxysilane, divinyl monochloro-isobutoxysilane.
Further, the molecular weight of the first raw material is 200-10000 g/mol; the molecular weight of the second raw material is 144-450 g/mol.
Further, in the step 2, the reducing agent is at least one of lithium aluminum hydride, lithium hydride, magnesium hydride, sodium hydride and red aluminum. The amount of the reducing agent is preferably 1-66% of the mass of the first intermediate product, wherein Y is completely reduced to hydrogen atoms and is slightly excessive. Preferably, lithium aluminum hydride is used, the preferable using amount is 6-44% of the mass of the first intermediate product, the reduction temperature is preferably-20-60 ℃, and the reduction time is preferably 1-5 h.
Further, in the step 3, the solid-liquid separation treatment is any one of standing for 4-10 hours, centrifugal treatment for 100-1000 s and ultrasonic treatment for 5000-10000 s.
Further, the silicon-hydrogen bond content of the polycarbosilane with high silicon-hydrogen content prepared in the step 4 is 1.0-2.4 mol/100 g.
Further, the aluminum content of the polyaluminum carbosilane is 0.01-1.01 mol/100 g.
Further, in step 5, the aluminum-containing compound is at least one of polyaluminum chloride, diisobutylaluminum hydride, aluminum fluoride, aluminum tripolyphosphate, aluminum sulfide, aluminum tartrate, aluminum tert-butoxide, aluminum dichloride, aluminum glycollate, aluminum trimethyl, dimethylaluminum chloride, aluminum triacetylacetonate, aluminum acetate, diethylaluminum iodide, lithium tri-tert-butoxyaluminum hydride, aluminum tris (4-methyl-8-hydroxyquinoline), aluminum isopropoxide, aluminum acrylate, aluminum triethoxide, and aluminum triphenyl.
The invention also provides polyaluminocarbosilane which is prepared by the preparation method and has the molecular weight of 300-18000 g/mol. Preferably, the molecular weight of the polyaluminum carbosilane is 342-5819 g/mol.
Further, the viscosity of the polyaluminocarbosilane is 15-1643 cp.
Furthermore, the aluminum content of the polyaluminocarbosilane is 0.01-1.01 mol/100g and is adjustable, and the content of silicon hydrogen in the polyaluminocarbosilane is high and is adjustable and can be 0.7-2.3 mol/100 g.
Furthermore, the content of silicon-hydrogen bonds of the polyaluminum carbosilane is 0.7-1.40 mol/100g, and the content of aluminum of the polyaluminum carbosilane is 0.1-1.01 mol/100 g. The polyaluminum carbosilane can be dehydrogenated and self-crosslinked.
Furthermore, the content of silicon-hydrogen bonds of the polyaluminum carbosilane is 1.40-2.3 mol/100g, the content of aluminum is 0.01-0.55 mol/100g, and the polyaluminum carbosilane can be dehydrogenated and self-crosslinked.
Further, the yield of the ceramic at 1000 ℃ is higher than 80% after the polyaluminocarbosilane is dehydrogenated and self-crosslinked.
Further, the yield of the ceramic at 1000 ℃ after the polyaluminocarbosilane is dehydrogenated and self-crosslinked is 90%.
Further, the polyaluminocarbosilane can be dehydrogenated and self-crosslinked to obtain solid polyaluminocarbosilane.
The invention has the following beneficial effects:
1. the invention takes silane containing silicon-hydrogen bond as a first raw material to carry out hydrosilylation reaction with a second raw material to obtain a first intermediate product, wherein the second raw material contains 1 or 2 CH2CH-bonded silane, and at least two Y are attached to the silicon atom in the second starting material, said Y being selected from: the method comprises the steps of preparing polycarbosilane with high silicon hydrogen content, preparing a silicon hydride by using the polycarbosilane, preparing a silicon hydride solution, preparing at least one of ethoxy, methoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, Cl, Br and I, reducing Y to form a silicon hydrogen bond, introducing at least two silanes capable of being reduced to the silicon hydrogen bond into a first raw material when one silicon hydrogen bond is consumed by the first raw material to synthesize a first intermediate product, performing reduction reaction on the first intermediate product to obtain a second intermediate product, performing solid-liquid separation treatment on the second intermediate product to obtain a third intermediate product, replacing the first raw material with the third intermediate product, and performing silicon hydrogen addition, reduction reaction and solid-liquid separation treatment in sequence to obtain the polycarbosilane with high silicon hydrogen content, and preparing the high silicon hydrogen contentThe content of polycarbosilane reacts with an aluminum-containing compound to prepare the polyaluminocarbosilane. The content of aluminum in the polyaluminocarbosilane is high and adjustable and can be 0.01-1.01 mol/100g, the content of silicon hydrogen in the polyaluminocarbosilane aluminum is high and adjustable and can be 0.7-2.3 mol/100g, and the content of silicon hydrogen and the content of aluminum in the polyaluminocarbosilane can be simultaneously far higher than the content of silicon hydrogen and the content of aluminum in polyaluminocarbosilane prepared by the prior art, so the polyaluminocarbosilane aluminum can be used as a raw material for preparing silicon carbide ceramics with high aluminum-containing elements.
2. In the process of preparing the polyaluminum carbosilane, the solid waste is less and is only 0.014-1.5 of the product quality.
3. The liquid polyaluminum carbosilane prepared by the method of the invention can be prepared without using a solvent. In the preparation process of preparing the solid polyaluminum carbosilane, the dosage of the solvent is less and the waste liquid is less.
4. The prepared poly-aluminum carbon silane can contain a large amount of active groups-silicon hydrogen bonds, can be dehydrogenated and added to form new poly-carbon silane, and has good solubility.
5. The polyaluminum carbosilane prepared by the invention can contain two active groups, namely a silicon-hydrogen bond and a C ═ C bond, can be subjected to dehydrogenation addition or hydrosilylation, and the softening point and the self-crosslinking temperature of the product can be regulated and controlled by controlling the addition degree.
Detailed Description
It is worth mentioning that: the terms "first", "second", and the like in the present invention are used for clearly describing the technical solutions, and are not limitations of the technical solutions.
The invention will be further illustrated with reference to specific examples:
[ EXAMPLES one ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 20 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time is 30h, so as to prepare the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 1;
the mass ratio of the first raw material to the second raw material is 1: 1.1;
the first raw material is 100g of polycarbosilane (obtained by pyrolysis of polydimethylsiloxane, and can be referred to as the literature: Chengxianzhen, metabolism and Songyuan, etc.. the influence of the reaction temperature on the performance of high-pressure synthesis of the polycarbosilane from the polydimethylsiloxane [ J ] the high molecular report, 2005(06): 851-one 855.), and the content of a silicon-hydrogen bond is 0.7mol/100 g;
the molecular weight of the first raw material is 800, and the softening point is 20 ℃;
the second raw material is vinyl trichlorosilane (sold in markets);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 23.29g of lithium aluminum hydride to the first intermediate product, reacting at-20 ℃ for 20 hours, and reducing the Y into a hydrogen atom to prepare a second intermediate product;
step 3, standing the second intermediate product for 60 hours to realize solid-liquid separation, removing 93.79g of solid, and then carrying out reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene is 1:1, the mass ratio of the third intermediate product to the second raw material is 1:2.73, 57.85g of lithium aluminum hydride is added, 232.91g of solid is removed, and thus a solution of polycarbosilane with high silicon-hydrogen content is prepared.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with aluminum tert-butoxide, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the aluminum tert-butoxide is 1: 1.87, reacting at 360 ℃ for 50h to obtain the polyaluminum carbosilane.
The molecular weight of the polyaluminum carbosilane is 1456, the silicon-hydrogen bond content of the polyaluminum carbosilane is 0.83mol/100g, and the aluminum content of the polyaluminum carbosilane is 0.78mol/100 g.
[ example two ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 20 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time 30h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 1;
the mass ratio of the first raw material to the second raw material is 1: 0.8;
the first raw material is 100g of polycarbosilane (obtained by pyrolysis of polydimethylsiloxane, and can be referred to as the literature: Chengxianzhen, metabolism and Songyuan, etc.. the influence of the reaction temperature on the performance of high-pressure synthesis of the polycarbosilane from the polydimethylsiloxane [ J ] the high molecular report, 2005(06): 851-one 855.), and the content of a silicon-hydrogen bond is 0.7mol/100 g;
the molecular weight of the first raw material is 800, and the softening point is 20 ℃;
the second starting material was divinyldichlorosilane (commercially available);
it is noted that, in this embodiment, the first raw material is dropped into the mixture of the second raw material and the solvent cyclohexane to control only one ethylene group in the divinyl dichlorosilane to perform hydrosilylation reaction, and the other ethylene group is remained;
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 11.92g of lithium aluminum hydride into the first intermediate product, reacting at 0 ℃ for 10 hours, and reducing the Y into a hydrogen atom to obtain a second intermediate product;
step 3, centrifuging the second intermediate product for 1000s to realize solid-liquid separation, removing 48.0g of solid, and then carrying out reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene was 1:1.5, the mass ratio of the third intermediate product to the second raw material was 1:1.51, 22.53g of lithium aluminum hydride, and 90.70g of solids were removed, thereby obtaining a solution of polycarbosilane having a high silicon-hydrogen content.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with aluminum tert-butoxide, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the aluminum tert-butoxide is 1: 0.91 at the reaction temperature of 280 ℃ for 40h to obtain the polyaluminum carbosilane.
The molecular weight of the polyaluminum carbosilane is 1683, the silicon-hydrogen bond content of the polyaluminum carbosilane is 0.89mol/100g, and the aluminum content of the polyaluminum carbosilane is 0.45mol/100 g.
[ EXAMPLE III ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 20 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time 30h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 4;
the mass ratio of the first raw material to the second raw material is 1: 0.54;
the first raw material is 100g of polycarbosilane (obtained by pyrolysis of polydimethylsiloxane, and can be referred to as the literature: Chengxianzhen, metabolism and Songyuan, etc.. the influence of the reaction temperature on the performance of high-pressure synthesis of the polycarbosilane from the polydimethylsiloxane [ J ] the high molecular report, 2005(06): 851-one 855.), and the content of a silicon-hydrogen bond is 0.7mol/100 g;
the molecular weight of the first raw material is 800, and the softening point is 20 ℃;
the second raw material is vinyl trichlorosilane (sold in markets);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 11.44g of lithium aluminum hydride to the first intermediate product, reacting at 20 ℃ for 10 hours, and reducing the Y into a hydrogen atom to prepare a second intermediate product;
step 3, standing the second intermediate product for 10 hours to realize solid-liquid separation, removing 46.04g of solid, and then carrying out reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene was 1:4, the mass ratio of the third intermediate product to the second raw material was 1:1.91, 40.45g of lithium aluminum hydride, and 162.87g of solid was removed to obtain a solution of polycarbosilane having a high silicon-hydrogen content.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with aluminum tert-butoxide, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the aluminum tert-butoxide is 1: 0.82, the reaction temperature is 60 ℃, and the polyaluminum carbosilane is prepared after 10 hours of reaction.
The molecular weight of the polyaluminum carbosilane is 2517, the silicon-hydrogen bond content of the polyaluminum carbosilane is 1.36mol/100g, and the aluminum content of the polyaluminum carbosilane is 0.41mol/100 g.
[ EXAMPLE IV ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 20 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time 30h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 2;
the mass ratio of the first raw material to the second raw material is 1: 0.44;
the first raw material is 100g of polycarbosilane (obtained by pyrolysis of polydimethylsiloxane, and can be referred to as the literature: Chengxianzhen, metabolism and Songyuan, etc.. the influence of the reaction temperature on the performance of high-pressure synthesis of the polycarbosilane from the polydimethylsiloxane [ J ] the high molecular report, 2005(06): 851-one 855.), and the content of a silicon-hydrogen bond is 0.7mol/100 g;
the molecular weight of the first raw material is 1656, and the softening point is 200 ℃;
the second raw material is vinyl trichlorosilane (sold in markets);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 9.32g of lithium aluminum hydride into the first intermediate product, reacting at 40 ℃ for 10 hours, and reducing the Y into a hydrogen atom to obtain a second intermediate product;
step 3, standing the second intermediate product for 10 hours to realize solid-liquid separation, removing 37.52g of solid, and then carrying out reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene was 1:1, the mass ratio of the third intermediate product to the second raw material was 1:1.65, 34.91g of lithium aluminum hydride, and 140.56g of solid was removed to obtain a solution of polycarbosilane having a high silicon-hydrogen content.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with aluminum tert-butoxide, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the aluminum tert-butoxide is 1:0.5, the reaction temperature is 100 ℃, and the reaction time is 300 hours, thereby preparing the polyaluminum carbosilane.
The molecular weight of the polyaluminum carbosilane is 3614, the silicon-hydrogen bond content of the polyaluminum carbosilane is 0.93mol/100g, and the aluminum content of the polyaluminum carbosilane is 0.5mol/100 g.
[ EXAMPLE V ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 20 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time 30h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 2;
the mass ratio of the first raw material to the second raw material is 1: 0.9;
the first raw material is 100g of polyaluminum carbosilane, and the content of silicon-hydrogen bonds is 0.45mol/100 g;
the molecular weight of the first raw material is 1656, and the softening point is 200 ℃;
the second raw material is propenyl trichlorosilane (sold in the market);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 17.54g of lithium aluminum hydride to the first intermediate product, reacting at 50 ℃ for 8h, and reducing the Y into a hydrogen atom to prepare a second intermediate product;
step 3, performing ultrasonic treatment on the second intermediate product for 10s to realize solid-liquid separation, removing 70.61g of solid, and performing reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene is 1:1, the mass ratio of the third intermediate product to the second raw material is 1:2.15, 41.85g of lithium aluminum hydride is added, 168.48g of solid is removed, and thus a solution of polycarbosilane with high silicon-hydrogen content is prepared.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with aluminum tert-butoxide, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the aluminum tert-butoxide is 1:1, reacting at 200 ℃ for 50 hours to obtain the polyaluminum carbosilane.
The molecular weight of the polyaluminum carbosilane is 4312, the silicon-hydrogen bond content of the polyaluminum carbosilane is 0.7mol/100g, and the aluminum content of the polyaluminum carbosilane is 1.01mol/100 g.
[ EXAMPLE six ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 20 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time 30h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 5;
the mass ratio of the first raw material to the second raw material is 1: 0.9;
the first raw material is 100g of polyaluminum carbosilane, and the content of silicon-hydrogen bonds is 0.45mol/100 g;
the molecular weight of the first raw material is 1656, and the softening point is 200 ℃;
the second raw material is vinyl trichlorosilane (sold in markets);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 19.06g of lithium aluminum hydride to the first intermediate product, reacting at 120 ℃ for 6h, and reducing the Y into a hydrogen atom to prepare a second intermediate product;
step 3, centrifuging the second intermediate product for 100s to realize solid-liquid separation, removing 76.74g of solid, and then carrying out reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene is 1:1, the mass ratio of the third intermediate product to the second raw material is 1:1.85, 39.23g of lithium aluminum hydride is added, 157.96g of solid is removed, and thus a solution of polycarbosilane with high silicon-hydrogen content is prepared.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with aluminum triethoxide, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the aluminum triethoxide is 1:1.6, the reaction temperature is 180 ℃, and the reaction time is 50 hours, so that the polyaluminum carbosilane is prepared.
The molecular weight of the polyaluminum carbosilane is 3897, the silicon-hydrogen bond content of the polyaluminum carbosilane is 0.71mol/100g, and the aluminum content of the polyaluminum carbosilane is 0.9mol/100 g.
[ EXAMPLE VII ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 20 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time 30h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 5;
the mass ratio of the first raw material to the second raw material is 1: 0.9;
the first raw material is 100g of polyaluminum carbosilane, and the content of silicon-hydrogen bonds is 0.45mol/100 g;
the molecular weight of the first raw material is 1656, and the softening point is 200 ℃;
the second raw material is vinyl trichlorosilane (sold in markets);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 19.06g of lithium aluminum hydride to the first intermediate product, reacting at 120 ℃ for 6h, and reducing the Y into a hydrogen atom to prepare a second intermediate product;
step 3, centrifuging the second intermediate product for 100s to realize solid-liquid separation, removing 76.74g of solid, and then carrying out reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene is 1:1, the mass ratio of the third intermediate product to the second raw material is 1:1.85, 39.23g of lithium aluminum hydride is added, 157.96g of solid is removed, and thus a solution of polycarbosilane with high silicon-hydrogen content is prepared.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with aluminum triethoxide, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the aluminum triethoxide is 1:1.6, the reaction temperature is 280 ℃, and the reaction time is 50 hours, so that the polyaluminum carbosilane is prepared.
The molecular weight of the polyaluminum carbosilane is 5617, the silicon-hydrogen bond content of the polyaluminum carbosilane is 0.91mol/100g, and the aluminum content of the polyaluminum carbosilane is 1.01mol/100 g.
[ example eight ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 150 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time is 10h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 2;
the mass ratio of the first raw material to the second raw material is 1: 0.8;
the first raw material is 100g of poly beryllium carbosilane, and the content of a silicon-hydrogen bond is 0.65mol/100 g;
the molecular weight of the first raw material is 1661, and the softening point is 190 ℃;
the second raw material is propenyl trichlorosilane (sold in the market);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 24.36g of lithium aluminum hydride to the first intermediate product, reacting at 80 ℃ for 4 hours, and reducing the Y into a hydrogen atom to obtain a second intermediate product;
step 3, performing ultrasonic treatment on the second intermediate product for 8000s to realize solid-liquid separation, removing 98.08g of solid, and performing reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene is 1:1, the mass ratio of the third intermediate product to the second raw material is 1:2.80, 54.51g of lithium aluminum hydride is added, 219.49g of solid is removed, and thus a solution of polycarbosilane with high silicon-hydrogen content is prepared.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with triphenylaluminum, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the triphenylaluminum is 1: 2.6, the reaction temperature is 120 ℃, and the reaction time is 50 hours, so that the polyaluminum carbosilane is prepared.
The molecular weight of the polyaluminum carbosilane is 1983, the silicon-hydrogen bond content of the polyaluminum carbosilane is 1.01mol/100g, and the aluminum content of the polyaluminum carbosilane is 1.01mol/100 g.
[ EXAMPLE ninth ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the hydrosilylation is a normal pressure continuous reaction method, the reaction temperature is 250 ℃, and the platinum dosage is 1.87 multiplied by 10- 2mmol/g, reaction time 10h, thereby obtaining the first intermediateA product;
the mass ratio of the first raw material to the solvent xylene is 1: 6;
the mass ratio of the first raw material to the second raw material is 1: 0.8;
the first raw material is 100g of poly beryllium carbosilane, and the content of a silicon-hydrogen bond is 0.65mol/100 g;
the molecular weight of the first raw material is 1661, and the softening point is 190 ℃;
the second raw material is propenyl trichlorosilane (sold in the market);
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 24.36g of lithium aluminum hydride to the first intermediate product, reacting at 80 ℃ for 4 hours, and reducing the Y into a hydrogen atom to obtain a second intermediate product;
step 3, performing ultrasonic treatment on the second intermediate product for 8000s to realize solid-liquid separation, removing 98.08g of solid, and performing reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene is 1:1, the mass ratio of the third intermediate product to the second raw material is 1:2.80, 54.51g of lithium aluminum hydride is added, 219.49g of solid is removed, and thus a solution of polycarbosilane with high silicon-hydrogen content is prepared.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with triphenylaluminum, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the triphenylaluminum is 1: 0.3, the reaction temperature is 60 ℃, and the reaction time is 10 hours, thereby preparing the polyaluminum carbosilane.
The molecular weight of the polyaluminum carbosilane is 651, the content of silicon-hydrogen bonds of the polyaluminum carbosilane is 2.3mol/100g, and the content of aluminum of the polyaluminum carbosilane is 0.01mol/100 g.
[ EXAMPLE eleven ]
A preparation method of polyaluminum carbosilane comprises the following steps:
step 1, synthesizing a first intermediate product;
carrying out hydrosilylation on a first raw material and a second raw material to obtain a first intermediate product;
the silicon-hydrogen addition reaction is a normal-pressure continuous reaction method, the reaction temperature is 200 ℃, and the platinum dosage is 5.87 multiplied by 10- 2mmol/g, reaction time 5h, thus obtaining the first intermediate product;
the mass ratio of the first raw material to the solvent xylene is 1: 10;
the mass ratio of the first raw material to the second raw material is 1: 0.95;
the first raw material is 100g of poly zirconium carbon silane, and the content of silicon hydrogen bonds is 0.65mol/100 g;
the molecular weight of the first raw material is 1583, and the softening point is 173 ℃;
the second starting material was divinyldichlorosilane (commercially available);
it is noted that, in this embodiment, the first raw material is dropped into the mixture of the second raw material and the solvent cyclohexane to control only one ethylene group in the divinyl dichlorosilane to perform hydrosilylation reaction, and the other ethylene group is remained;
step 2, reducing the first intermediate product to prepare a second intermediate product;
adding 14.16g of lithium aluminum hydride into the first intermediate product, reacting for 1h at 100 ℃, and reducing the Y into a hydrogen atom to prepare a second intermediate product;
step 3, performing ultrasonic treatment on the second intermediate product for 1000s to realize solid-liquid separation, removing 57.0g of solid, and performing reduced pressure distillation at 20 ℃ to remove the solvent to obtain a third intermediate product;
and 4, replacing the first raw material in the step 1 with 100g of the third intermediate product, and sequentially performing the steps 1, 2 and 3, wherein the reaction temperature and the reaction time are unchanged, and the materials or the mixture ratio of the materials is as follows: the mass ratio of the third intermediate product to the solvent xylene was 1:10, the mass ratio of the third intermediate product to the second raw material was 1:1.51, 22.46g of lithium aluminum hydride, and 90.42g of solids were removed, thereby obtaining a solution of polycarbosilane having a high silicon-hydrogen content.
And 5, reacting the solution of the polycarbosilane with high silicon hydrogen content prepared in the step 4 with triphenylaluminum, wherein the mass ratio of the polycarbosilane with high silicon hydrogen content to the triphenylaluminum is 1: 0.26, the reaction temperature is 360 ℃, and the reaction time is 50 hours, so that the polyaluminum carbosilane is prepared.
The molecular weight of the polyaluminum carbosilane is 5613, the silicon-hydrogen bond content of the polyaluminum carbosilane is 0.8mol/100g, and the aluminum content of the polyaluminum carbosilane is 0.1mol/100 g.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (9)
1. A preparation method of polyaluminum carbosilane is characterized by comprising the following steps: the method comprises the following steps:
step 1, carrying out hydrosilylation reaction on a first raw material and a second raw material at a mass ratio of 1: 0.1-3.2 at 20-200 ℃ for 1-30 h to prepare a first intermediate product;
step 2, adding a reducing agent into the first intermediate product, and reacting for 2-20 hours at-20-120 ℃ to obtain a second intermediate product;
step 3, carrying out solid-liquid separation treatment on the second intermediate product, and removing solids after solid-liquid separation to obtain a third intermediate product;
step 4, replacing the first raw material in the step 1 with the third intermediate product, and sequentially repeating the step 1, the step 2 and the step 3 to obtain polycarbosilane with high silicon-hydrogen content;
step 5, mixing the polycarbosilane with high silicon-hydrogen content prepared in the step 4 and an aluminum-containing compound according to the mass ratio of 1: 0.01-8, reacting for 0.5-50 h at 60-360 ℃ to obtain the polyaluminum carbosilane;
wherein the first raw material is polycarbosilane and/or polysilane containing Si-H; the second raw material contains (X) nSi (Y) m; x is CH2Is CH-A-or CH2A is at least one of acyl, acyloxy, saturated alkyl and cycloalkyl; y is at least one of Cl, Br, I and alkoxy, the sum of n and m is equal to 3 or 4, n is one of 1 or 2, and m is 2 or 3.
2. The method for preparing polyaluminocarbosilane as claimed in claim 1, wherein: in the step 1, a solvent is added during the hydrosilylation reaction of a first raw material and a second raw material, and the mass ratio of the first raw material to the solvent is 1: 0-3.5.
3. The method for preparing polyaluminocarbosilane as claimed in claim 2, wherein: the solvent is at least one of xylene, toluene and cyclohexane.
4. The method for preparing polyaluminocarbosilane as claimed in claim 1, wherein: the molecular weight of the first raw material is 200-10000 g/mol; the molecular weight of the second raw material is 144-450 g/mol.
5. The method for preparing polyaluminocarbosilane as claimed in claim 1, wherein: in step 2, the reducing agent is at least one of lithium aluminum hydride, lithium hydride, magnesium hydride, sodium hydride and red aluminum.
6. The method for preparing polyaluminocarbosilane as claimed in claim 1, wherein: in step 5, the aluminum-containing compound is at least one of polyaluminum chloride, diisobutylaluminum hydride, aluminum fluoride, aluminum tripolyphosphate, aluminum sulfide, aluminum tartrate, aluminum tert-butoxide, aluminum dichloride, aluminum glycollate, aluminum trimethyl, dimethylaluminum chloride, aluminum triacetylacetonate, aluminum acetate, aluminum diethyliodide, lithium tri-tert-butoxyaluminum hydride, aluminum tris (4-methyl-8-hydroxyquinoline), aluminum isopropoxide, aluminum acrylate, aluminum triethoxide and aluminum triphenyl.
7. The method for preparing polyaluminocarbosilane as claimed in claim 1, wherein: the aluminum content of the polyaluminum carbosilane is 0.01-1.01 mol/100 g.
8. A polyaluminocarbosilane prepared by the process of any one of claims 1 to 7, wherein: the molecular weight of the polyaluminum carbosilane is 342-5819 g/mol.
9. A polyaluminocarbosilane as defined in claim 8 wherein: the content of the silicon-hydrogen bond of the polyaluminum carbosilane is 0.7-2.3 mol/100 g.
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