CN112250874B - Preparation method of polyborocarbosilane - Google Patents
Preparation method of polyborocarbosilane Download PDFInfo
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- CN112250874B CN112250874B CN202011173321.3A CN202011173321A CN112250874B CN 112250874 B CN112250874 B CN 112250874B CN 202011173321 A CN202011173321 A CN 202011173321A CN 112250874 B CN112250874 B CN 112250874B
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Abstract
The invention provides a preparation method of polyborocarbosilane, which comprises the steps of firstly synthesizing a first raw material containing-C ═ C silane; adding a certain catalyst into the first raw material and the second raw material to obtain a first intermediate product through olefin metathesis reaction, wherein the second raw material contains (X) nSi (Y) m; x is CH2＝CH－CH2-or CH2CH-; y is at least one of Cl, Br, I and alkoxy; adding a reducing agent into the first intermediate product, reducing the Y into hydrogen atoms by the reducing agent, and removing solids in the first intermediate product to obtain a second intermediate product; and finally, reacting the second intermediate product with a boron-containing compound to obtain the polyborocarbosilane. The polyborocarbosilane prepared by the method has high boron content and adjustable boron content.
Description
Technical Field
The invention relates to a preparation method of silane, in particular to a preparation method of polyborocarbosilane.
Background
The boron-containing silicon carbide fiber shows huge application potential due to the outstanding high temperature resistance (Liwenhua, Wangjun, Wanghao and the like. research progress of a precursor conversion method boron-containing continuous SiC fiber, aerospace material technology, 2007,4: 5-7.).
The Sylramic fiber is typical of boron-containing fiber, the preparation process is various, firstly, boron is introduced in the preparation process through the boron-containing atmosphere without melting, and the defects are obvious: the boron-containing atmosphere has high requirements on the corrosion resistance of equipment, and the treatment of toxic waste gas is also difficult. In the second preparation process, a boron-containing precursor is used, and the defects are obvious: the polyborosilazane precursor is extremely easy to hydrolyze and oxidize, the synthesis of the precursor and the whole fiber preparation process must be completed in an anhydrous and oxygen-free environment, and the platform construction and production cost is extremely high.
In the invention with application number 201911043861.7, in a closed reaction container, the poly-silicon carbosilane and the boron-containing monomer are subjected to synthetic reaction at high temperature and high pressure to generate boron-containing poly-carbon silane coarse material, wherein the poly-silicon carbosilane is a low molecular product of polydimethylsiloxane after pyrolysis, is in a liquid state at room temperature, and has a molecular weight of less than 1000 g/mol; dissolving and filtering the boron-containing polycarbosilane coarse material to obtain a spinning-grade boron-containing polycarbosilane precursor; and carrying out melt spinning, non-melting, high-temperature sintering and sintering treatment on the spinning-grade boron-containing polycarbosilane precursor to obtain the boron-containing silicon carbide fiber. The disadvantages are obvious: boron is introduced through dehydrogenation reaction of silicon hydrogen bond and boron hydrogen, the silicon hydrogen bond is consumed to obtain the silicon boron bond, the prepared boron-containing polycarbosilane has low silicon hydrogen content, the root is that the silicon hydrogen content of the polycarbosilane is low (0.58mol/100g), the method is limited by the silicon hydrogen content, the introduced boron element is limited, and the high boron content polyborosilane cannot be obtained.
In the invention of application No. 201510192019.5, the boron-containing monomer (R)2BH and RBH2) The boron-containing polycarbosilane Precursor (PBCS) is prepared by reacting with low molecular weight polycarbosilane, boron is introduced through dehydrogenation reaction of silicon-hydrogen bond and boron hydrogen, silicon-boron bond is obtained by consuming silicon-hydrogen bond, the prepared boron-containing polycarbosilane has low silicon-hydrogen content and is limited by silicon-hydrogen content, and the method introducesThe boron element of (a) is also limited.
Disclosure of Invention
The invention aims to provide a preparation method of polyborocarbosilane, and particularly provides polyborocarbosilane with the boron content of 0.1-2.1 mol/100 g.
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
hydrosilylation of a silane containing a silicon-hydrogen bond with an organic compound containing at least two-C to obtain a first starting material or
Halogenating silicon-hydrogen bond in silane containing silicon-hydrogen bond, coupling with vinyl Grignard reagent and/or monohalopropenyl Grignard reagent, separating to remove solid salt to obtain first raw material containing-C ═ C silane or
Firstly, halogenating a silicon-hydrogen bond in silane containing the silicon-hydrogen bond, then carrying out sodium condensation on the silicon-hydrogen bond and monohalogenated ethylene and/or allyl, and then separating and removing solid salt to obtain a first raw material containing-C silane;
step 2, synthesizing a first intermediate product,
performing olefin metathesis reaction on the first raw material and the second raw material by adding a catalyst to obtain a first intermediate product;
the olefin double decomposition reaction temperature is 30-220 ℃, the reaction time is 30-750 hours, and the mass ratio of the first raw material to the second raw material is 1: 0.2-6;
the second raw material is silane containing (X) nSi (Y) m; x is CH2＝CH-CH2-or CH2CH-; y is at least one of Cl, Br, I and alkoxy, the sum of n and m is equal to any one of 2,3 and 4, n and m are positive integers, and the molecular weight of the second raw material is 144-450;
step 3, reducing the first intermediate product to prepare a second intermediate product,
adding a reducing agent into the first intermediate product, reacting for 2-60 h at-10-60 ℃, reducing the Y into hydrogen atoms, separating to remove solids to obtain a second intermediate product,
step 4, reacting the second intermediate product obtained in the step 3 with a boron-containing compound to obtain the polyborocarbosilane,
the mass ratio of the second intermediate product to the boron-containing compound is 1: 0.1-1.2, the reaction temperature is 20-360 ℃, and the reaction time is 0.5-50 h.
Further, in the step 1, the olefin double decomposition reaction is a cross double decomposition reaction, and the reaction temperature is 60-200 ℃.
Further, in step 2, the catalyst added in the olefin metathesis reaction is a high activity metal M-carbene and/or { (CF3)2MeCO } ]2(ArN) -M ═ CH (t-Bu) ], wherein M is Mo or W; the dosage of the catalyst is 10-10000 ppm.
Further, in the step 2, a catalyst added in the olefin metathesis reaction is a rhodium-or ruthenium-containing compound, and the amount of the catalyst is 10-10000 ppm.
Further, in step 2, the catalyst is RuCl2 (PPh)3)3、 RuHCI(CO)(PPh3)3、RuCI(SiMe3)(CO)(PPh3)2、[RhCl(cod)]2、 Ru＝CHPhCl2(PCy3)2、Ru＝CHPhCl2(PCy3)(SIMes)、[RhCl(cod)]2、 [Rh(OSiMe3)(cod)]2And [1, 3-bis (2, 4, 6-trimethylphenyl) -2-imidazolidinylidene]At least one of bis (2-bromopyridine) (phenylmethylene) ruthenium dichloride.
In step 3, 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 such that all Y is reduced to hydrogen atoms and a slight excess is provided, and the amount of the reducing agent is 1 to 66% by mass of the first intermediate product. 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 step 4, the boron-containing compound is at least one of borane, diborane, trichloroborazine, boric acid, tributyl borate, trimethyl borate, triethyl borate, 4- (ethylthio) phenylboronic acid, 4-bromobenzeneboronic acid, phenylboronic acid, tetraminodiborane, p-diphenylboronic acid, ethyldichloroborane, trimethylsilylacetyleneboronic acid, and borazane; but also solutions of borane complexes and/or solutions of boranes.
Further, in step 1, the first raw material containing — C ═ C silane can be prepared by hydrosilylation of polycarbosilane with tetraethenylsilane or tetraallylsilane.
Further, in step 1, the first starting material containing-C ═ C silane is prepared by the following method: firstly, halogenating hydrosilation of polycarbosilane, then reacting with a vinyl Grignard reagent and/or an allyl Grignard reagent, and separating to remove solid salt to obtain a first raw material containing-C ═ C silane, wherein the reaction temperature is-10-60 ℃, and the mass of the Grignard reagent is 1.2-1.8 times of that of the silicon-hydrogen bond in the polycarbosilane.
Further, in step 1, the first starting material containing-C ═ C silane is prepared by the following method: firstly, the hydrosilation of the polycarbosilane is halogenated, the hydrosilation reaction degree is 10-100%, then the polycarbosilane and monohalogenated ethylene and/or allyl are subjected to sodium condensation, and then the solid salt is removed through separation treatment, so that the first raw material of the silane containing-C ═ C is obtained, the reaction temperature is 30-90 ℃, and the mass amount of the monohalogenated ethylene and/or monohalogenated allyl is 1.2-1.8 times of that of silicon-chlorine bonds in the polycarbosilane.
Further, in the step 1, the silane containing a silicon-hydrogen bond is polycarbosilane and/or polysilane.
Further, the polysilane is LPS (polysilane, polydimethylsilane pyrolysis, silicon-hydrogen bond of 0.4 mol-0.5 mol/100 g).
And (2) when the silane is polysilane in the step (1), synthesizing polyborocarbosilane containing silicon-silicon bonds, and putting the polyborocarbosilane containing silicon-silicon bonds into an autoclave or an atmospheric pressure cracking device for pyrolysis reaction to obtain the polyborocarbosilane containing silicon-carbon bonds. Because the silicon-silicon bond has high activity and is difficult to store, such as easy hydrolysis, the polyborocarbosilane synthesized by taking polysilane as a raw material can be further pyrolyzed at high temperature to convert unstable silicon-silicon bonds in the polyborocarbosilane into stable silicon-carbon bonds, and meanwhile, the distribution of boron is not only at the periphery of molecules, the steric hindrance of boron is enlarged, and the stability is improved.
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).
Further, the polycarbosilane can also be polycarbosilane containing heterogeneous elements, such as PALCS (solid polyaluminocarbosilane, silicon hydrogen bond of 0.4mol to 0.5mol/100g), PZrCS (solid polyzircosilane, silicon hydrogen bond of 0.4mol to 0.5mol/100g), PBCS (solid polyborocarbosilane, silicon hydrogen bond of 0.4mol to 0.5mol/100g) with low boron content.
Furthermore, a solvent is added in the reaction of the first intermediate product and the boron-containing compound, the mass ratio of the first intermediate product to the boron-containing compound and the solvent is 1: 0.03-1.5: 0-5, and the solvent is toluene or xylene and the like. When the solvent is 0, the first intermediate product is liquid silane. When the solvent is other than 0, the first intermediate product is a solid silane, but may be a liquid silane.
The polyborocarbosilane is prepared by the method, and contains 0.1-2.1 mol/100g of boron.
The polyborocarbosilane is prepared by the method, and contains C-C bonds, wherein the content of the C-C bonds is 0.08-0.87 mol/100 g.
The polyborocarbosilane is prepared by the method, and after all Si-Y bonds are reacted, the polyborocarbosilane contains C-C bonds, and the content of the C-C bonds is 0.08-0.87 mol/100 g.
The polyborocarbosilane is prepared by the method, and after the Si-Y bond part is reacted, the polyborocarbosilane contains C-C bonds, and the content of the C-C bonds is 0.08-0.87 mol/100 g.
The polyborocarbosilane is prepared by the method, and after the C-C bond part is reacted, the polyborocarbosilane contains C-C bonds, and the content of the C-C bonds is 0.08-0.80 mol/100 g.
The polyborocarbosilane is prepared by the method, wherein C-C bonds and Si-Y bonds are all reacted, and the boron content of the polyborocarbosilane is 0.4-2.1 mol/100 g.
The polyborocarbosilane is prepared by the method, wherein C ═ C bonds and Si-Y bonds are partially reacted, the boron content of the polyborocarbosilane is 0.4-1.9 mol/100g, and the polyborocarbosilane contains C ═ C bonds and Si-Y bonds.
Further, a compound containing a nitrogen-containing hydrogen bond is added to the polyborocarbosilane containing an Si-Y bond, thereby obtaining the nitrogen-containing polyborocarbosilane. The mass ratio of the polyborocarbosilane to the nitrogen-containing hydrogen bond-containing compound is 1: 0.1-3, the temperature is-50-30 ℃, the time is 2-20 hours, and the nitrogen-containing hydrogen bond-containing compound can react with a C ═ C bond and/or a Si-Y bond.
Further, the compound containing the nitrogen-hydrogen bond is ammonia gas, ethylenediamine, hexamethyldisilazane, tetramethyldivinyldisilazane, dimethyltetravinyldisilazane, tetramethyldisilazane, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasilazane, at least one of 1, 3-diphenyltetramethyldisilazane, 1,2,3,4,5, 6-hexamethylcyclotrisilazane, 1,2,3,4,5,6,7, 8-octamethylcyclotetrasilazane, 1, 3-divinyl-1, 3-diphenyl-1, 3-dimethyldisilazane, bis (chloromethyl) tetramethyldisilazane, trivinyltrimethylcyclotrisilazane, N' tri-tert-butylsilanetriamine; also can be an ether solution of methylamine, an ether solution of ethylamine and an ether solution of aniline.
Particularly, nitrogen-containing or nitrogen-free polyborocarbosilane synthesized by polysilane is pyrolyzed in an autoclave or an atmospheric pressure cracking device to obtain polyborocarbosilane containing silicon-carbon bonds, the pyrolysis converts the silicon-silicon bonds in the polyborocarbosilane into the silicon-carbon bonds, the pyrolysis atmosphere is inert atmosphere, the temperature is 380-480 ℃, the time is 0.5-100 h, the content of silicon-hydrogen bonds of the polyborocarbosilane obtained by pyrolysis is 0.1-0.8 mol/100g, and the composition of the nitrogen-containing polyborocarbosilane obtained by pyrolysis is SiC1.40～,2.43H5.8～9.16O0.01～0.33B0.10～1.2Cl0～0.36N0～0.45The obtained polyborocarbosilane can be liquid or solid, and the content of silicon-hydrogen bonds is 0.1-0.7 mol/100 g.
The invention also provides a preparation method of the polyborocarbosilane, which comprises the following steps:
step 1, synthesizing a first raw material,
hydrosilylation of a silane containing a silicon-hydrogen bond with an organic compound containing at least two-C to obtain a first starting material or
Halogenating silicon-hydrogen bond in silane containing silicon-hydrogen bond, coupling with vinyl Grignard reagent and/or propenyl Grignard reagent, separating to remove solid salt to obtain first raw material containing-C ═ C silane or
Firstly halogenating a silicon-hydrogen bond in silane containing the silicon-hydrogen bond, then carrying out sodium condensation on the silicon-hydrogen bond and monohalogenated ethylene and/or monohalogenated propenyl, separating and removing solid salt to obtain a first raw material containing-C silane,
step 2, adding a catalyst into the first raw material and the second raw material according to the mass ratio of 1: 0.2-6, and reacting at 30-220 ℃ for 30-750 hours to obtain a first intermediate product;
the second raw material is silane containing (X) nSi (Y) m; x is CH2＝CH-CH2-or CH2CH-; y is at least one of Cl, Br, I and alkoxy, the sum of n and m is equal to any one of 2,3 and 4, and n and m are positive integers; the molecular weight of the second raw material is 144-450;
and 3, reacting the first intermediate product obtained in the step 2 with a boron-containing compound according to the mass ratio of 1: 0.1-1.2 at 10-420 ℃ for 0.5-30 h to obtain the polyborocarbosilane. The selection of the raw material substances of the method is the same as that of the preparation method of the polyborocarbosilane, and the obtained polyborocarbosilane can also react with a compound containing a nitrogen hydrogen bond to obtain the nitrogen-containing polyborocarbosilane, which is not described again.
Compared with the prior art, the invention has the following beneficial effects:
1. the method comprises the steps of firstly synthesizing silane containing-C as a first raw material, and then carrying out olefin metathesis reaction on the first raw material and silane containing (X) nSi (Y) m to obtain a first intermediate product, wherein X is CH2＝CH-CH2-or CH2Adding a reducing agent into the first intermediate product, reacting for 2-60 h at-10-60 ℃, reducing Y to hydrogen atoms, separating to remove solids to obtain a second intermediate product, and reacting the second intermediate product obtained in the step 3 with a boron-containing compound to prepare the polyborocarbosilane. the-C ═ C structure is introduced into polysilane or polycarbosilane, consuming one Si-h bond, while the introduced-C ═ C bond is 1 to 3, and after olefin metathesis reaction with silane containing (X) nsi (Y) m to obtain the first intermediate product, Y introduced into polysilane or polycarbosilane can be 3 to 9, more importantly, during this process, Si-h bond in polysilane or polycarbosilane is converted into-C ═ C, and the number of active groups is not consumed, C ═ C is also a group introduced by boron element, the number of active groups in polysilane or polycarbosilane is large, the types of active groups are changed into two types of Si-Y and-C ═ C, different types of active groups can be reacted separately, for example, -C ═ C bond can be borohydride and/or hydrosilylation, the polyborocarbosilane can also be self-polymerized, each Si-Y bond can react with a boron-containing compound, the introduction point of the boron-containing compound is multiplied, the amount of the introduced boron-containing compound is not influenced by the content of silicon hydrogen bonds in the raw material polysilane or polycarbosilane, the introduction amount of borane can also be controlled, and part of Si-Y bonds and-C ═ C are reserved, so that the polyborocarbosilane with high reaction activity is obtained. Therefore, the boron content of the polyborocarbosilane prepared by the method is high and can reach 0.1-2.1 mol/100 g.
2. The invention improves the preparation method of the polyborocarbosilane boron, firstly synthesizes silane containing-C ═ C as a first raw material, and then carries out olefin metathesis reaction on the first raw material and silane containing (X) nSi (Y) m to obtain a first intermediate product, wherein X is CH2＝CH-CH2-or CH2The first intermediate product obtained in the step 2 and the boron-containing compound are directly reacted for 0.5 to 30 hours at the temperature of 10 to 420 ℃ according to the mass ratio of 1:0.1 to 1.2The polyborocarbosilane should be prepared. According to the scheme, a silicon-hydrogen bond in polysilane or polycarbosilane is converted into-C, then olefin double decomposition reaction is carried out between-C, the C-C structure is kept, meanwhile, a plurality of silane chlorides are introduced, the silane-chlorine bond can directly react with a boron-containing compound, the silicon-chlorine bond is not required to be reduced into the silicon-hydrogen bond by adding a reducing agent, the high-boron-content polyborocarbosilane can be obtained, and the content can be regulated. The method simplifies the synthesis process and greatly saves the cost.
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 present invention will be further described with reference to the following examples.
[ EXAMPLES one ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
the preparation method comprises the steps of mixing polycarbosilane which is in a liquid state and has the reaction pressure of 12MPa, the molecular weight of 300 and the silicon-hydrogen bond content of 0.7mol/100g with 48.96g of tetravinylsilane, reacting at 90 ℃ for 300 hours, and then removing 8.16g of tetravinylsilane by reduced pressure distillation, wherein the catalyst is 880ppm chloroplatinic acid to obtain a first raw material containing silane with-C, the molecular weight of the first raw material is 368, and the vinyl content of the first raw material is 0.9 mol.
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
performing olefin metathesis reaction at the reaction temperature of 30 ℃ for 600 hours to obtain the first intermediate product;
adding 100ppm of RhCl (cod) into the first raw material and the second raw material]2Catalyzing the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 0.32;
the second raw material is vinyl trichlorosilane;
step 3, reducing the first intermediate product to prepare a second intermediate product;
6.27g of lithium aluminum hydride as a reducing agent is added into the first intermediate product, and after the reaction at 60 ℃ for 2 hours, the mixture is kept stand for 6 hours to remove solids, so that a second intermediate product is prepared.
And 4, reacting the second intermediate product prepared in the step 3 with boric acid, wherein the mass ratio of the second intermediate product to the boric acid is 1: 0.22, the reaction temperature is 300 ℃, and the reaction time is 0.5h, so that the polyborocarbosilane is prepared.
The polyborocarbosilane has the composition of SiC1.87H6.72O0.02B0.21The boron content was 0.35mol/100 g.
[ example two ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
mixing liquid polycarbosilane with the molecular weight of 300 and the silicon-hydrogen bond content of 0.7mol/100g and 114.24g of tetravinylsilane in an autoclave under the reaction pressure of 12MPa, reacting at 90 ℃ for 600h, and then removing 19.04g of tetravinylsilane by reduced pressure distillation, wherein the catalyst is chloroplatinic acid with the concentration of 10000ppm, so as to obtain a first raw material containing-C, the molecular weight of the first raw material is 434, and the vinyl content of the first raw material is 2.1 mol.
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
the olefin metathesis reaction is carried out in an autoclave, the reaction temperature is 160 ℃, and after 600 hours of reaction, the unreacted second raw material 292g is removed by reduced pressure distillation, so as to prepare the first intermediate product;
1000ppm of RhCl (cod) is added to the first raw material and the second raw material]2Catalyzing the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 0.97;
the second raw material is vinyl trichlorosilane;
step 3, reducing the first intermediate product to prepare a second intermediate product;
adding 18.81g of reducing agent lithium aluminum hydride into the first intermediate product, standing for 60 hours after reacting for 6 hours at 60 ℃, and removing solids to obtain a second intermediate product.
And 4, reacting the second intermediate product prepared in the step 3 with a boron-containing compound, wherein the mass ratio of the second intermediate product to the boron-containing compound is 1: 0.34, the reaction temperature is 280 ℃, and the time is 2 hours, and unreacted aluminum acrylate is distilled off, thereby preparing the polyborocarbosilane.
The polyborocarbosilane has the composition of SiC1.89H6.16O0.01B0.32The boron content was 0.52mol/100 g.
[ EXAMPLE III ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
100g of liquid polycarbosilane (obtained by pyrolysis of polydimethylsiloxane and having a molecular weight of 380 and a viscosity of 32cp and a silicon-hydrogen bond content of 0.7mol/100g, which can be referred to as a reference document: a royal oil bridge, songyuancai. the structural and performance characterization [ J ] of vinyl-containing liquid polycarbosilane [ 2010(02):20-23 ]) and 11.2g of dimethyl divinyl silane are reacted for 50 hours at a temperature of 20 ℃, and unreacted dimethyl divinyl silane 0.2g is removed by reduced pressure distillation, wherein the catalyst is 1ppm of chloroplatinic acid, so that a first raw material containing-C silane is obtained, and the first raw material has a molecular weight of 405 and a viscosity of 35 cp;
step 2, synthesizing a first intermediate product;
obtaining a first intermediate product by olefin metathesis reaction of a first raw material and a second raw material;
the olefin metathesis reaction temperature is 60 ℃, the reaction time is 30h,
10ppm of RhCl (cod) is added into the first raw material and the second raw material]2Catalyzing the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 2.26;
the second raw material is vinyl trichlorosilane;
step 3, reducing the first intermediate product to prepare a second intermediate product;
adding 43.89g of reducing agent lithium aluminum hydride into the first intermediate product, reacting for 50h at 0 ℃, reducing silicon-chlorine bonds into silicon-hydrogen bonds, standing for 10h, and removing solids to obtain a second intermediate product.
Step 4, reacting the second intermediate product obtained in the step 3 with boric acid to prepare the polyborocarbosilane,
the reaction temperature is 360 ℃, the reaction time is 50h, and the mass ratio of the second intermediate product to the boric acid is 1: 0.48.
the polyborocarbosilane has the composition of SiC1.92H5.48O0.01B0.45The boron content was 0.73mol/100 g.
[ EXAMPLE IV ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
100g of liquid polysilane (a byproduct of preparing polycarbosilane by pyrolysis of polydimethylsiloxane, and a main chain is a silicon-carbon bond) with molecular weight of 410 and viscosity of 26cp and with silicon-hydrogen bond content of 0.65mol/100g reacts with 112g of dimethyldivinylsilane at 60 ℃ for 600h, and 61.6g of unreacted dimethyldivinylsilane is removed by reduced pressure distillation, wherein the catalyst is 751ppm chloroplatinic acid, so that a first raw material containing-C ═ C is obtained, and the molecular weight of the first raw material is 568 and the viscosity of the first raw material is 29 cp;
step 2, synthesizing a first intermediate product;
obtaining a first intermediate product by olefin metathesis reaction of a first raw material and a second raw material;
the olefin metathesis reaction temperature is 167 ℃, the reaction time is 201h, 3000ppm Ru ═ CHPhCl is added into the first raw material and the second raw material2(PCy3)(SIMes) catalyzing the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 1.32;
the second raw material is propenyl trichlorosilane;
step 3, reducing the first intermediate product to prepare a second intermediate product;
28.21g of reducing agent lithium aluminum hydride is added into the first intermediate product, and after the mixture is reacted for 14 hours at 33 ℃, and is kept stand for 50 hours, a second intermediate product is prepared.
Step 4, reacting the second intermediate product obtained in the step 3 with boric acid to prepare the polyborocarbosilane,
the reaction temperature is 60 ℃, the reaction time is 10h, and the mass ratio of the second intermediate product to the boric acid is 1: 0.18.
the polyborocarbosilane has the composition of SiC1.57H5.58O0.05B0.69The boron content was 1.13mol/100 g.
[ EXAMPLE V ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
composition and structure analysis of solid polycarbosilane (obtained by pyrolysis of polydimethylsilane, and can be referred to in the literature: Chengxianzhen, Xiaojia Yuan, Xiexiang, etc.) with molecular weight of 300 and silicon-hydrogen bond content of 0.7mol/100g]The university of defense science and technology, 2005, 27(2):20-23.) was dissolved in 100g of xylene to form a solution, and Cl was added to the solution at 0.01L/min2Halogenating a silicon-hydrogen bond, wherein the reaction temperature during introduction is 45 ℃, introducing for 200min, adding 0.6mol of vinyl magnesium bromide for Grignard coupling, coupling at 6 ℃, washing for three times after coupling for 50h, and then carrying out reduced pressure distillation to remove xylene, thereby obtaining a first raw material containing-C, wherein the molecular weight of the first raw material is 343, and the vinyl content in the first raw material is 0.6 mol.
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
the olefin double decomposition reaction is carried out in a high-pressure kettle, the reaction temperature is 150 ℃, the reaction time is 450 hours, and the pressure is 8Mpa, so that the first intermediate product is prepared;
300ppm of RhCl (cod) is added into the first raw material and the second raw material]2Catalyzing the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 0.97;
the mass ratio of the first raw material to the solvent xylene is 1: 1;
the second raw material is propenyl trichlorosilane;
step 3, reducing the first intermediate product to prepare a second intermediate product;
adding 18.81g of reducing agent lithium aluminum hydride into the first intermediate product, reacting for 6h at 60 ℃, reducing silicon-chlorine bonds into silicon-hydrogen bonds, standing for 15h, and removing solids to obtain a solution of a second intermediate product.
Step 4, reacting the second intermediate product obtained in the step 3 with boric acid to prepare the polyborocarbosilane,
the reaction temperature is 300 ℃, the reaction time is 0.5h, and the mass ratio of the second intermediate product to the boric acid is 1: 0.32.
the polyborocarbosilane has the composition of SiC1.76H9.51O0.01B1.33The boron content was 1.81mol/100 g. The content of the silicon-hydrogen bond is 0.39mol/100 g.
[ EXAMPLE six ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
dissolving 100g of solid polyaluminocarbosilane with molecular weight of 1700 and silicon-hydrogen bond content of 0.45mol/100g in 100g of dimethylbenzene to form a solution, and introducing Cl into the solution at 0.01L/min2Halogenating a silicon-hydrogen bond, introducing the reaction temperature of 60 ℃, introducing for 200min, adding 0.3mol of vinyl magnesium bromide for Grignard coupling, coupling the reaction temperature of 10 ℃, washing for three times after coupling for 60h, distilling off xylene by organic phase under reduced pressure to obtain a first raw material containing-C, wherein the molecular weight of the first raw material is 1760, and the vinyl content in the first raw material is0.3mol。
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
the olefin double decomposition reaction is carried out in a high-pressure reaction kettle at the reaction temperature of 100 ℃ and the pressure of 6Mpa, and the solvent is removed by reduced pressure distillation after the reaction is carried out for 600 hours, so as to prepare the first intermediate product;
1000ppm of RhCl (cod) is added to the first raw material and the second raw material]2Catalyzing the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 2.16;
the mass ratio of the first raw material to the solvent xylene is 1: 10;
the second raw material is vinyl trichlorosilane;
step 3, reducing the first intermediate product to prepare a second intermediate product;
adding 43.89g of reducing agent lithium aluminum hydride into the first intermediate product, reacting for 50h at 0 ℃, reducing a silicon-chlorine bond into a silicon-hydrogen bond, standing for 5h, removing solids to prepare a solution of a second intermediate product, and distilling the solution of the second intermediate product at 80 ℃ under reduced pressure to separate out the solvent to obtain the second intermediate product.
Step 4, reacting the second intermediate product obtained in the step 3 with boric acid to prepare the polyborocarbosilane,
the reaction temperature is 100 ℃, the reaction time is 1h, and the mass ratio of the second intermediate product to the boric acid is 1: 0.17.
the polyborocarbosilane has the composition of SiC1.70H7.72O0.01B0.67The boron content is 1.06mol/100g, and the silicon-hydrogen bond content is 1.59mol/100 g.
[ EXAMPLE VII ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
100g of solid polycarbosilane with the molecular weight of 1600 and the silicon-hydrogen bond content of 100g of 0.7mol/100g is dissolved in 100g xylene, and introducing Cl at 0.1L/min2Halogenating a silicon-hydrogen bond, wherein the reaction temperature during introduction is 65 ℃, after 600min introduction, adding 0.8mol of sodium, introducing chloroethylene into the solution under the stirring condition, carrying out Wutz reaction, reacting at the temperature of 40 ℃ for 50h, washing with water for three times, and distilling off xylene by organic phase vacuum distillation, thereby obtaining a first raw material containing-C, wherein the molecular weight of the first raw material is 1691, and the vinyl content of the first raw material is 0.59 mol.
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
performing olefin double decomposition reaction in a high-pressure reaction kettle at the reaction temperature of 180 ℃ and the pressure of 13Mpa, and performing reduced pressure distillation to remove the solvent after the reaction is performed for 600 hours, thereby preparing the first intermediate product;
adding 3000ppm of a high activity metal-carbene (Mo) to the first feedstock and the second feedstock to catalyze the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 2.6; the mass ratio of the first raw material to the solvent xylene is 1: 10; the second raw material is vinyl trichlorosilane;
step 3, reducing the first intermediate product to prepare a second intermediate product;
adding 43.89g of reducing agent lithium aluminum hydride into the first intermediate product, reacting for 50h at 0 ℃, reducing silicon-chlorine bonds into silicon-hydrogen bonds, centrifuging for 30min, removing solids to obtain a solution of a second intermediate product, and distilling the solution of the second intermediate product at 45 ℃ under reduced pressure to separate out the solvent to obtain the second intermediate product.
Step 4, reacting the second intermediate product obtained in the step 3 with boric acid to prepare the polyborocarbosilane,
the reaction temperature is 230 ℃, the reaction time is 4h, and the mass ratio of the second intermediate product to the boric acid is 1: 0.54.
the polyborocarbosilane has the composition of SiC1.47H4.59O0.01B0.45Boron containsThe amount was 0.81mol/100 g.
[ example eight ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
dissolving 100g of solid polycarbosilane with the molecular weight of 1600 and the silicon-hydrogen bond content of 0.7mol/100g in 100g of dimethylbenzene to form a solution, and introducing Cl into the solution at 0.1L/min2Halogenating a silicon-hydrogen bond, wherein the reaction temperature during introduction is 65 ℃, after 600min introduction, adding 0.8mol of sodium, introducing chloroethylene into the solution under the stirring condition, carrying out Wutz reaction, reacting at the temperature of 40 ℃ for 50h, washing with water for three times, and distilling off xylene by organic phase vacuum distillation, thereby obtaining a first raw material containing-C, wherein the molecular weight of the first raw material is 1691, and the vinyl content of the first raw material is 0.59 mol.
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
performing olefin double decomposition reaction in a high-pressure reaction kettle at the reaction temperature of 180 ℃ and the pressure of 13Mpa, and performing reduced pressure distillation to remove the solvent after the reaction is performed for 600 hours, thereby preparing the first intermediate product;
adding 3000ppm of a high activity metal-carbene (Mo) to the first feedstock and the second feedstock to catalyze the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 0.33; the mass ratio of the first raw material to the solvent xylene is 1: 10; the second raw material is vinyl trichlorosilane;
step 3, reacting the first intermediate product obtained in the step 2 with boric acid to prepare the polyborocarbosilane,
the reaction temperature is 420 ℃, the reaction time is 20h, and the mass ratio of the first intermediate product to the boric acid is 1: 0.1.
the polyborocarbosilane has the composition of SiC1.87H7.03O0.33B0.10The boron content was 0.16mol/100 g.
[ EXAMPLE ninth ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
dissolving 100g of solid polycarbosilane with the molecular weight of 1600 and the silicon-hydrogen bond content of 0.7mol/100g in 100g of dimethylbenzene to form a solution, and introducing Cl into the solution at 0.1L/min2Halogenating a silicon-hydrogen bond, wherein the reaction temperature during introduction is 65 ℃, after 600min introduction, adding 0.8mol of sodium, introducing chloroethylene into the solution under the stirring condition, carrying out Wutz reaction, reacting at the temperature of 40 ℃ for 50h, washing with water for three times, and distilling off xylene by organic phase vacuum distillation, thereby obtaining a first raw material containing-C, wherein the molecular weight of the first raw material is 1691, and the vinyl content of the first raw material is 0.59 mol.
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
performing olefin double decomposition reaction in a high-pressure reaction kettle at the reaction temperature of 180 ℃ and the pressure of 13Mpa, and performing reduced pressure distillation to remove the solvent after the reaction is performed for 600 hours, thereby preparing the first intermediate product;
adding 3000ppm of a high activity metal-carbene (Mo) to the first feedstock and the second feedstock to catalyze the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 2.06; the mass ratio of the first raw material to the solvent xylene is 1: 10; the second raw material is vinyl trichlorosilane;
step 3, reacting the first intermediate product obtained in the step 2 with diborane to prepare the polyborocarbosilane,
the reaction temperature is 60 ℃, the reaction time is 3h, and the mass ratio of the first intermediate product to diborane is 1: 0.18.
the polyborocarbosilane has the composition of SiC1.48H6.67O0.04B1.35The boron content was 1.99mol/100 g.
[ EXAMPLE eleven ]
A preparation method of polyborocarbosilane comprises the following steps:
step 1, synthesizing a first raw material,
the preparation method comprises the steps of mixing liquid polysilane with the reaction pressure of 12MPa, the molecular weight of 300 and the silicon-hydrogen bond content of 0.45mol/100g with 80g of tetravinylsilane, reacting at 120 ℃ for 100h, and then removing 18.8g of tetravinylsilane by reduced pressure distillation, wherein the catalyst is chloroplatinic acid of 60ppm to obtain a first raw material containing-C, the molecular weight of the first raw material is 398, and the vinyl content of the first raw material is 1.5 mol.
Step 2, synthesizing a first intermediate product;
100g of a first raw material and a second raw material are subjected to olefin metathesis reaction to obtain a first intermediate product;
the olefin metathesis reaction is carried out in an autoclave, the reaction temperature is 100 ℃, after the reaction is carried out for 300 hours, 358g of unreacted second raw material is removed by reduced pressure distillation, and thus the first intermediate product is prepared;
adding 100ppm of RhCl (cod) into the first raw material and the second raw material]2Catalyzing the olefin metathesis reaction;
the mass ratio of the first raw material to the second raw material is 1: 6;
the second raw material is vinyl trichlorosilane;
and 3, reacting the first intermediate product prepared in the step 2 with diborane, wherein the mass ratio of the second intermediate product to the diborane is 1: 0.45, the reaction temperature is 75 ℃, and the reaction time is 1h, thus obtaining the polyborocarbosilane containing silicon-silicon bonds.
The polyborocarbosilane has the composition of SiC1.89H8.78O0.04Cl0.41B1.2The boron content was 1.4mol/100g, and no C ═ C bond was contained.
[ example eleven ]
A method of preparing a polyborocarbosilane comprising:
100g of the polyborocarbosilane synthesized in the example and 10g of dimethylamine are put into a reaction bottle and reacted for 20 hours at the temperature of minus 50 ℃ under normal pressure to obtain the nitrogen-containing polyborocarbosilane, the composition of which is SiC1.99H8.73O0.04B1.2Cl0.36N0.24The boron content was 1.4mol/100g, and the nitrogen content was 0.024 mol/100 g.
[ EXAMPLE twelfth ]
A method of preparing a polyborocarbosilane comprising:
100g of the polyborocarbosilane synthesized in example ten and 300g of dimethylamine are put into a reaction bottle and reacted for 20 hours at 30 ℃ under normal pressure to obtain the nitrogen-containing polyborocarbosilane with the composition of SIC2.43H9.16O0.04B1.2N0.38The boron content was 1.4mol/100g and the nitrogen content was 0.67 mol/100 g.
[ EXAMPLE thirteen ]
A method of preparing a polyborocarbosilane comprising:
100g of the polyborocarbosilane synthesized in the example and 100g of dimethylamine are put into a reaction bottle and reacted for 5 hours at 0 ℃ under normal pressure to obtain the nitrogen-containing polyborocarbosilane, the composition of which is SiC2.43H9.16O0.04B1.2N0.21Cl0.14The boron content was 1.4mol/100g and the nitrogen content was 0.33mol/100 g.
[ example fourteen ]
A method of preparing a polyborocarbosilane comprising:
the polyborocarbosilane synthesized in the embodiment eleven is subjected to pyrolysis reaction in a high-pressure kettle, and the polyborocarbosilane containing silicon-carbon bonds is obtained after the closed reaction for 10 hours at 480 ℃ and under the pressure of 30Mpa, and the composition of the polyborocarbosilane is SiC1.53H8.72O0.04B1.2N0.07Boron content of 1.5mol/100g, nitrogen content of 0.01mol/100g, silicon hydrogen content of 0.61mol/100g, molecular weight of 4597, softening point 300 ℃.
The polyborocarbosilane does not contain silicon-silicon bonds and C ═ C bonds, is stable in property, is stored in a sealed mode, cannot be denatured after 3 months, such as self-crosslinking and hydrolysis, is exposed in the air, and cannot be hydrolyzed within 24 hours.
[ example fifteen ]
A method of preparing a polyborocarbosilane comprising:
the polyborocarbosilane synthesized in example twelve was placed in an autoclaveCarrying out pyrolysis reaction, and carrying out closed reaction at 430 ℃ and 10Mpa for 50h to obtain polyborocarbosilane containing silicon-carbon bonds, wherein the composition of the polyborocarbosilane is SiC1.53H8.73O0.04B1.2N0.45Boron content of 1.5mol/100g, nitrogen content of 0.74mol/100g, silicon hydrogen content of 0.77mol/100g, molecular weight of 976, softening point of 64 ℃.
The polyborocarbosilane does not contain silicon-silicon bonds and C ═ C bonds, is stable in property, is stored in a sealed mode, cannot be denatured after 3 months, such as self-crosslinking and hydrolysis, is exposed in the air, and cannot be hydrolyzed within 24 hours.
[ example sixteen ] to
The polyborocarbosilane synthesized in the thirteen embodiment is put into a high-pressure kettle for pyrolysis reaction, and the polyborocarbosilane containing silicon-carbon bonds is obtained after the closed reaction for 100 hours at 400 ℃ and 5Mpa, and the composition of the polyborocarbosilane is SiC1.53H8.73O0.04B1.2N0.45Boron content of 1.5mol/100g, nitrogen content of 0.74mol/100g, silicon hydrogen content of 0.79mol/100g, molecular weight of 613, softening point of 29 ℃.
The polyborocarbosilane does not contain silicon-silicon bonds and C ═ C bonds, is stable in property, is stored in a sealed mode, cannot be denatured after 3 months, such as self-crosslinking and hydrolysis, is exposed in the air, and cannot be hydrolyzed within 24 hours.
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 method for preparing polyborocarbosilane, comprising:
step 1, synthesizing a first raw material,
hydrosilylation of polycarbosilanes and/or polysilanes with organic compounds containing at least two-C ═ C to give a first starting material or
Halogenating silicon-hydrogen bond in silane containing silicon-hydrogen bond, coupling with vinyl Grignard reagent and/or propenyl Grignard reagent, separating to remove solid salt to obtain first raw material containing-C ═ C silane or
Firstly, halogenating a silicon-hydrogen bond in silane containing the silicon-hydrogen bond, then carrying out sodium condensation on the silicon-hydrogen bond and monohalogenated ethylene and/or monohalogenated propylene, and then separating and treating to remove solid salt to obtain a first raw material containing-C silane;
step 2, carrying out olefin metathesis reaction on the first raw material and the second raw material by adding a catalyst to obtain a first intermediate product;
the olefin double decomposition reaction temperature is 30-220 ℃, the reaction time is 30-750 hours, and the mass ratio of the first raw material to the second raw material is 1: 0.2-6;
the second raw material is silane containing (X) nSi (Y) m; x is CH2＝CH-CH2-or CH2CH-; y is at least one of Cl, Br, I and alkoxy, the sum of n and m is equal to any one of 2,3 and 4, and n and m are positive integers;
step 3, adding a reducing agent into the first intermediate product, reacting for 2-60 hours at-10-60 ℃, and separating to remove solids to obtain a second intermediate product;
and 4, reacting the second intermediate product obtained in the step 3 with a boron-containing compound according to the mass ratio of 1: 0.1-1.2 at 20-360 ℃ for 0.5-50 h to obtain the polyborocarbosilane.
2. The method of claim 1, wherein the method comprises the steps of: in the step 2, the olefin double decomposition reaction is a cross double decomposition reaction, and the reaction temperature is 60-200 ℃.
3. The method of claim 1, wherein the method comprises the steps of: in the step 2, the catalyst is high-activity metal M-carbene, wherein M is Mo or W, and the dosage of the catalyst is 10-10000 ppm.
4. The method of claim 1, wherein the method comprises the steps of: in the step 2, the catalyst is a rhodium or ruthenium-containing compound, and the dosage of the catalyst is 10-10000 ppm.
5. The method of claim 1, wherein the method comprises the steps of: in step 3, the reducing agent is at least one of lithium aluminum hydride, lithium hydride, magnesium hydride, sodium hydride and red aluminum.
6. The method of claim 1, wherein the method comprises the steps of: in step 4, the boron-containing compound is at least one of borane, diborane, trichloroborazine, boric acid, tributyl borate, trimethyl borate, triethyl borate, 4- (ethylthio) phenylboronic acid, 4-bromobenzeneboronic acid, phenylboronic acid, tetramethyiaminodiborane, p-diphenylboronic acid, ethyldichloroborane, trimethylsilylacetyleneboronic acid and borazane.
7. The process for producing a polyborocarbosilane as claimed in any one of claims 1 to 6, wherein: adding a nitrogen-containing hydrogen bond compound into the polyborocarbosilane, and reacting for 2-20 h at-50-30 ℃ to obtain nitrogen-containing polyborocarbosilane; the mass ratio of the polyborocarbosilane to the nitrogen-containing hydrogen bond-containing compound is 1: 0.1-3.
8. The method of claim 7, wherein the polyborocarbosilane is prepared by the following steps: the nitrogen-hydrogen bond-containing compound is at least one of ammonia gas, ethylenediamine, hexamethyldisilazane, tetramethyldivinyldisilazane, dimethyltetravinyldisilazane, tetramethyldisilazane, 1,3,5, 7-tetramethyl-1, 3,5, 7-tetravinylcyclotetrasilazane, 1, 3-diphenyltetramethyldisilazane, 1,2,3,4,5, 6-hexamethylcyclotrisilazane, 1,2,3,4,5,6,7, 8-octamethylcyclotetrasilazane, 1, 3-divinyl-1, 3-diphenyl-1, 3-dimethyldisilazane, bis (chloromethyl) tetramethyldisilazane, trivinyltrimethylcyclotrisilazane, and N, N' -tri-tert-butylsilanetriamine.
9. A method for preparing polyborocarbosilane, comprising:
step 1, synthesizing a first raw material,
hydrosilylation of polycarbosilanes and/or polysilanes with organic compounds containing at least two-C ═ C to give a first starting material or
Halogenating silicon-hydrogen bond in silane containing silicon-hydrogen bond, coupling with vinyl Grignard reagent and/or propenyl Grignard reagent, separating to remove solid salt to obtain first raw material containing-C ═ C silane or
Firstly halogenating a silicon-hydrogen bond in silane containing the silicon-hydrogen bond, then carrying out sodium condensation on the silicon-hydrogen bond and monohalogenated ethylene and/or monohalogenated propenyl, separating and removing solid salt to obtain a first raw material containing-C silane,
step 2, adding a catalyst into the first raw material and the second raw material according to the mass ratio of 1: 0.2-6, and reacting at 30-220 ℃ for 30-750 hours to obtain a first intermediate product; an olefin metathesis reaction occurs between the first feedstock and a second feedstock;
the second raw material is silane containing (X) nSi (Y) m; x is CH2＝CH-CH2-or CH2CH-; y is at least one of Cl, Br, I and alkoxy, the sum of n and m is equal to any one of 2,3 and 4, and n and m are positive integers;
and 3, reacting the first intermediate product obtained in the step 2 with a boron-containing compound according to the mass ratio of 1: 0.1-1.2 at 10-420 ℃ for 0.5-30 h to obtain the polyborocarbosilane.
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