CN114395259A - Organic silicon composition and application thereof - Google Patents
Organic silicon composition and application thereof Download PDFInfo
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- CN114395259A CN114395259A CN202111503738.6A CN202111503738A CN114395259A CN 114395259 A CN114395259 A CN 114395259A CN 202111503738 A CN202111503738 A CN 202111503738A CN 114395259 A CN114395259 A CN 114395259A
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- 239000000203 mixture Substances 0.000 title claims abstract description 57
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052710 silicon Inorganic materials 0.000 title abstract description 13
- 239000010703 silicon Substances 0.000 title abstract description 13
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 47
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 43
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003381 stabilizer Substances 0.000 claims abstract description 32
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 30
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- 230000000694 effects Effects 0.000 claims abstract description 6
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 38
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- 229920005573 silicon-containing polymer Polymers 0.000 claims description 18
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- INFDPOAKFNIJBF-UHFFFAOYSA-N paraquat Chemical compound C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 INFDPOAKFNIJBF-UHFFFAOYSA-N 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
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Abstract
The invention belongs to the technical field of organic silicon, and relates to an organic silicon composition, which comprises an organic silicon polymer and a stabilizer; the organic silicon polymer is polycarbosilane containing unsaturated groups, and the stabilizer is a compound capable of consuming free radicals or reducing the activity of the free radicals. The organic silicon composition has the characteristics of good storage stability in room-temperature air environment, high organic silicon polymer content, wide applicability to organic silicon polymer structures and capability of being converted into silicon carbide ceramics.
Description
Technical Field
The invention belongs to the technical field of organic silicon, and relates to an organic silicon composition and application thereof.
Background
The ceramic material has the advantages of high hardness, high temperature resistance, stable physical and chemical properties and the like, and is applied to various fields of aerospace, industry, chemical industry and the like. The traditional ceramic powder forming method relates to the processes from micro powder preparation, forming (including the modes of rolling, extrusion molding, dry pressing, isostatic pressing, pouring, injection and the like), sintering (including the modes of hot-pressing sintering, reaction sintering, normal-pressure sintering, atmosphere pressure sintering, hot isostatic pressing sintering, spark plasma sintering and the like) to processing and the like. However, such conventional methods still have limitations that are difficult to overcome, including: the method has the defects of difficulty in obtaining uniform chemical components, poor finishing property, difficulty in manufacturing complex components, difficulty in solving the intrinsic brittleness problem of the ceramic material and the like, and influences the expansion of the application field of the ceramic material.
The organic silicon precursor conversion method for preparing the ceramic takes organic silicon polymer which can be converted into the ceramic through high-temperature pyrolysis as a raw material, and the organic silicon polymer is converted into the ceramic through high-temperature pyrolysis after being formed. The method breaks through some defects of the traditional ceramic powder metallurgy preparation technology, and also has a plurality of advantages: such as molecular designability, thereby realizing the regulation and control of ceramic composition, structure and performance; the mature processing technology and equipment of the transplantable high polymer material are used for the molding of ceramic materials, so that ceramic fibers, ceramic coatings, complex ceramic components and the like which are difficult to obtain by the traditional powder technology can be prepared; the ceramic can be realized at a lower temperature, and the production energy consumption and the cost are reduced; the complex, large and near-net-shape high-strength fiber reinforced ceramic matrix composite material can be prepared by a dipping-cracking process, and becomes a revolutionary technology for forming and manufacturing high-performance ceramics. Silicone polymers that have been reported to be convertible to ceramics include polysiloxanes, polysilazanes, polyborosilanes, polyborosilazanes, polysilacarbonimidamides, and the like.
The key point of preparing ceramic by organosilicon precursor conversion method is whether to prepare proper organosilicon polymer. The ideal silicone polymer for conversion to ceramic should possess the following properties: easy storage, good stability, low content of impurity elements, high ceramic yield, easy processing and forming, low price, no toxicity or low toxicity and the like.
Polycarbosilane is an organic silicon high molecular compound, the main chain of which is composed of silicon and carbon atoms alternately, the silicon and carbon atoms are connected with hydrogen or organic groups, the molecular chain is a linear or branched structure, and the silicon carbide ceramic can be converted through high-temperature treatment. The structure is simply [ (SiH)2CH2)x(SiHRCH2)y]n(R is an unsaturated group; x, y and n are numerical values greater than 0) or polycarbosilane with a branched structure thereof, has high ceramic yield and good fluidity, is easy to mold, and can be used for preparing materials such as silicon carbide ceramic-based composite materials, porous silicon carbide, 3D printing silicon carbide and the like. However, the ceramic precursor has poor stability and is easy to crosslink and solidify at room temperature. In order to prolong the storage period of the organic silicon polymer, the prior art generally adopts low-temperature refrigeration and changes the structure of the organic silicon polymer. For example, the Starfire related liquid polycarbosilane product (sold under the trade name SMP-10, which is an allyl-containing polycarbosilane) requires vacuum storage, inert atmosphere storage, or refrigeration. The use is inconvenient, and the contact with air is inevitable in the use process. China patent CN104177621 believes that the polycarbosilane contains rich SiH3The terminal group is liable to self-polycondensation or react with moisture in the air to generate hydrogen during storage, resulting in an increase in viscosity, which is disadvantageous for safe and stable storage. For extended shelf life, ring structures are introduced to control SiH3Group content. But the proposal has high requirements on the structure of the organic silicon polymer and has limited application range.
Disclosure of Invention
Aiming at the current situation of the prior art, the invention provides an organosilicon composition easy to store, which has the characteristics of good storage stability in room-temperature air environment, high organosilicon polymer content, wide applicability to organosilicon polymer structures and capability of being converted into silicon carbide ceramics.
One aspect of the present invention provides a silicone composition comprising a silicone polymer and a stabilizer; the organic silicon polymer is polycarbosilane containing unsaturated groups; the stabilizer is a compound capable of consuming free radicals or reducing the activity of free radicals.
Preferably, the silicone polymer has a structural unit represented by the following formula (1), formula (2), formula (3), and formula (4):
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10Independently of each other, is selected from one of C1-C6 alkyl and unsaturated group, but R1、R2、R3、R4、R5、R6、R7、R8、R9、R10At least one of which is selected from unsaturated groups and the structural unit in which it is present in the silicone polymer structure.
The structural formula is shown in the specification, wherein the formula (1) is represented by a structural formula of-CSiH 3; formula (2) is a structural formula representation of the structure-C2 SiH 2; formula (3) is expressed by the structural formula of-C3 SiH.
The C1-C6 alkyl can be C1-C6 straight-chain alkane or C3-C6 branched-chain alkane.
Preferably, the unsaturated group is a C ═ C and/or C ≡ C containing unsaturated group.
Preferably, the C ═ C and/or C ≡ C containing unsaturated group is a vinyl, ethynyl, propargyl, or allyl group.
Preferably, the silicone polymer does not include C1-C6 alkyl groups.
Experimental research shows that for the organosilicon polymer containing unsaturated groups and Si-H groups, which is easy to crosslink and cure in the air environment at room temperature, the influence of moisture on crosslinking and curing is limited under neutral conditions, the stability is also good under inert atmosphere, and the existence of oxygen is presumed to be a decisive factor for the crosslinking and curing in the air environment at room temperature. Further studies have found that the main cause of easy crosslinking in room temperature air environment is not self-condensation after oxidation of Si-H, but presumably the formation of free radicals and initiation of crosslinking of unsaturated groups in the structure. Based on the above experimental design and analysis, it was found that the storage stability of the silicone polymer at room temperature in the air environment can be improved by adding a stabilizer that can consume free radicals or reduce the activity of free radicals.
When the organosilicon polymer does not contain C1-C6 alkyl groups and only contains H and unsaturated groups containing C ═ C and/or C ≡ C, the storage stability of the organosilicon polymer in the room-temperature air environment can still be effectively improved by adding the stabilizer to the organosilicon polymer.
When the content of Si-H groups in the-CSiH 3 structure in the organic silicon polymer accounts for more than 10% of the total amount of all Si-H groups, the stabilizer is added into the organic silicon polymer, so that the storage stability of the organic silicon polymer in the room-temperature air environment can be effectively improved.
When the content of Si-H groups in the-CSiH 3 structure in the organic silicon polymer accounts for more than 30 percent of the total amount of all Si-H groups, the storage stability of the organic silicon polymer in the room-temperature air environment can still be effectively improved by adding the stabilizer into the organic silicon polymer.
When the content of Si-H groups in the-CSiH 3 structure in the organic silicon polymer accounts for more than 50% of the total amount of all Si-H groups, the storage stability of the organic silicon polymer in the room-temperature air environment can still be effectively improved by adding the stabilizer into the organic silicon polymer.
Preferably, the stabilizer is one or more selected from aromatic amine compounds, phenolic compounds, quinone compounds, nitro compounds and nitroso compounds.
Preferably, the stabilizer is a phenolic compound. The phenolic compound is easily oxidized, thereby consuming oxygen absorbed by the organic silicon polymer, and the oxidation product quinones of the phenolic compound have the capacity of combining with free radicals, thereby obviously improving the storage stability of the organic silicon polymer.
Preferably, the phenolic compound is a polyhydric phenol having two or more phenolic hydroxyl groups, and more preferably, the phenolic compound is a polyhydric phenol having an alkyl substituent. Examples of the polyhydric phenol having an alkyl substituent include one or more of 5-tert-butylcis-benzenetriol, 4-propylcatechol, 4-tert-butylcatechol, 2, 5-di-tert-butylhydroquinone, and 2, 5-di-tert-amylhydroquinone. The presence of alkyl substituents in the phenolic compound helps to improve the solubility of the polyhydric phenol in the silicone polymer.
Preferably, the stabilizer is a phenolic compound and a quinone compound in a mass ratio of (1-3): 1, mixing the mixture. The quinone compound is added into the phenolic compound, so that the formed free radicals can be captured earlier, and the storage stability of the organic silicon polymer is further improved.
Preferably, the quinone compound is a quinone compound having an alkyl substituent. Examples of the quinone compound having an alkyl substituent include one or more of 2, 5-di-tert-butyl-1, 4-benzoquinone, 2, 5-di-tert-butyl-o-phenylenediquinone, and 2, 5-di-tert-pentyl-1, 4-benzoquinone. The presence of alkyl substituents in the quinone compounds helps to improve the solubility of the quinone compounds in the organosilicon polymer.
Preferably, the mass of the stabilizer and the mass of the silicone polymer are related to each other by: 0% < mass of stabilizer/mass of organosilicon polymer less than or equal to 1%.
Preferably, the mass of the stabilizer and the mass of the silicone polymer are related to each other by: the mass of the stabilizer is more than 0 percent/the mass of the organic silicon polymer is less than or equal to 0.2 percent. The storage stability of the silicone polymer can be significantly improved by the addition of a small amount of stabilizer.
Preferably, the silicone composition further includes a ceramic filler or a metal compound filler. Ceramic fillers or metal compound fillers may be cited as particles or whiskers of silicon carbide, silicon nitride, silica, alumina, yttria, boron nitride, boron carbide, zirconia.
Another aspect of the present invention provides the use of a silicone composition that converts to a silicon carbide ceramic material upon pyrolysis at high temperatures, the silicon carbide ceramic material including, but not limited to, silicon carbide ceramic matrix composites, porous silicon carbide, silicon carbide tie layer materials, silicon carbide coatings, for the preparation of silicon carbide ceramics.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, a compound capable of consuming free radicals or reducing the activity of the free radicals is added into the organic silicon polymer containing unsaturated groups and Si-H groups as a stabilizer, so that the storage stability of the organic silicon polymer in the air environment at room temperature can be improved;
(2) the stabilizer with the content less than or equal to 1 percent is added into the organic silicon polymer containing unsaturated groups and Si-H groups, and the stabilizing effect is obvious under the condition of adding a small amount of the stabilizer;
(3) the method comprises the following steps of adding a phenolic compound and a quinone compound into an organic silicon polymer containing an unsaturated group and a Si-H group according to the mass ratio (1-3): 1 as a stabilizer, the mixture has better storage stability compared with a stabilizer added with a single component;
(4) the technical scheme of adding the stabilizer effectively avoids harsh conditions such as low-temperature storage of the organic silicon polymer, storage or use in an air-isolated environment and the like, and reduces dependence on related equipment;
(5) the storage stability of the organic silicon polymer is improved, so that the service life of the organic silicon polymer is prolonged, and the processing difficulty and economic loss caused by viscosity increase or curing during storage are reduced;
(6) the invention has wide applicability to the structure of the organic silicon polymer, small addition amount of the stabilizer and obvious effect, and does not influence the application of converting the organic silicon polymer into the silicon carbide ceramic by high-temperature pyrolysis.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of an allyl-containing polycarbosilane as described in comparative example 1 of the present invention;
FIG. 2 is an IR spectrum of an allyl group-containing polycarbosilane of comparative example 1 of the present invention before and after being left in an air atmosphere at 35 ℃ for 24 hours;
FIG. 3 is a graph showing the change in mass with time of an allyl-containing polycarbosilane of the present invention as compared to example 2, when it is incubated in an air atmosphere at 40 ℃;
FIG. 4 is a graph showing the change in mass with time of an allyl-containing polycarbosilane of the present invention as compared to example 3 when it is incubated in an air atmosphere at 50 ℃;
FIG. 5 is a nuclear magnetic hydrogen spectrum of an allyl-containing polycarbosilane as described in comparative example 4 of the present invention;
FIG. 6 is a nuclear magnetic hydrogen spectrum of a vinyl-containing polycarbosilane as described in comparative example 5 of the present invention;
FIG. 7 is a nuclear magnetic hydrogen spectrum of ethynyl and allylpolycarbosilane containing polymers as described in comparative example 6 of the present invention;
FIG. 8 is a plot of complex viscosity versus shear rate for the silicone compositions described in examples 1-4 of the present invention;
FIG. 9 is an X-ray diffraction pattern of a 1600 ℃ cleavage product of a silicone composition according to example 4 of the present invention;
FIG. 10 is a silicon carbide fiber reinforced silicon carbide composite tube obtained in example 23 of the present invention;
FIG. 11 shows the porous silicon carbide block and the internal morphology according to example 24 of the present invention;
fig. 12 is a compressive stress-strain curve of a porous silicon carbide block obtained in example 24 of the present invention.
Detailed Description
The technical solutions of the present invention are further described and illustrated by the following specific embodiments and the accompanying drawings, it should be understood that the specific embodiments described herein are only for the purpose of facilitating understanding of the present invention, and are not intended to limit the present invention specifically, and the drawings used herein are only for better illustrating the present disclosure and do not limit the scope of protection.
Comparative example 1
With Cl1.25(CH3O)1.75SiCH2Cl, chloropropene and the like are taken as raw materials, and according to the preparation method of US7714092B2, liquid polycarbosilane containing allyl is synthesized through Grignard reaction and reduction reaction, the number average molecular weight is 922, the weight average molecular weight is 2490, and the nuclear magnetic hydrogen spectrum is shown in figure 1. According to nuclear magnetic hydrogen spectrum, the structure of the material comprises three structural units (structural formula (1), structural formula (2) and structural formula (3)) as shown in the specification and an unsaturated group allyl; further, nuclear magnetic silicon spectrum shows that the structure thereof contains the structural unit (4) shown in the specification. Wherein, the structural formula (1), the structural formula (2) and the structural formula (3) are threeThe integral ratio of Si-H groups in the structural unit was 3.91: 4.09: 1, the content of Si-H groups in the structural formula (1) was 43.4% of the content of all Si-H groups. The molar ratio of allyl groups to Si-H groups is 1: 20.7.
the allyl-containing liquid polycarbosilane is heated at 80 ℃ for 24 hours in a nitrogen atmosphere, and no visible change is found in viscosity, nuclear magnetism and infrared spectrum. After separation by addition of 5% by weight of water under nitrogen and stirring at 35 ℃ for 24 hours, no visible changes were observed in the viscosity, nuclear magnetism and infrared spectra of the liquid allyl group-containing polycarbosilane. Placing the allyl-containing liquid polycarbosilane in a 35 ℃ blast oven, gelling after 24h, wherein no bubbles appear after gelling. The infrared spectra before and after the placement thereof are shown in fig. 2, and the infrared absorption peak associated with the unsaturated double bond is found to be significantly reduced.
Comparative example 2
The allyl group-containing liquid polycarbosilane having the structure shown in comparative example 1 was placed in a 40 ℃ forced air oven, gelled and embrittled after 10 hours, and no bubbles appeared after gelation. The mass change in the heat preservation process is monitored by adopting thermal weight loss, as shown in figure 3, when the temperature is preserved at 40 ℃, the mass is gradually reduced along with the prolonging of the heat preservation time, but the reduction range is not large, and the mass retention rate is 98.68 percent after 10 hours. And the oxygen content change is detected by adopting elemental analysis, and the elemental analysis shows that the oxygen content in the sample is 1.60 wt% before the heat preservation at 40 ℃, and the oxygen content is 3.81 wt% after 10 h. In the process of heat preservation, the phenomena of oxygen content increase and weight increase caused by more oxidation of Si-H groups in the allyl-containing liquid polycarbosilane structure do not occur. But the ir spectrum showed a significant reduction in the ir absorption peak associated with the unsaturated double bond.
Comparative example 3
The allyl group-containing liquid polycarbosilane having the structure shown in comparative example 1 was placed in a 50 ℃ forced air oven, and gelled and became brittle after 6 hours, and no bubbles appeared after gelation. The change of mass during the heat preservation process is monitored by adopting TGA, as shown in figure 4, when the heat preservation is carried out at 50 ℃, the mass gradually decreases with the prolonging of the heat preservation time, but the decrease amplitude is not large, and the mass retention rate is 98.65 percent after 6 hours. And the change of the oxygen content is detected by adopting elemental analysis, and the elemental analysis shows that the oxygen content is 3.61 wt% after the heat preservation is carried out for 6 hours at the temperature of 50 ℃, and the oxygen content before the heat preservation is 1.60 wt%. In the heat preservation process at 50 ℃, the phenomena of oxygen content increase and weight increase caused by more oxidation of Si-H groups in the structure do not occur. But the ir spectrum also shows a significant reduction in the ir absorption peak associated with the unsaturated double bond.
Comparative example 4
With Cl0.5(CH3O)2.5SiCH2Cl, chloropropene and the like are taken as raw materials, and according to the preparation method of US7714092B2, liquid polycarbosilane containing allyl is synthesized through Grignard reaction and reduction reaction, the number average molecular weight is 1462, the weight average molecular weight is 9642, and the nuclear magnetic hydrogen spectrum is shown in figure 5. The integral ratio of Si-H groups in the three structural units of structural formula (1), structural formula (2) and structural formula (3) was 3.82: 1.91: 1, the content of Si-H groups in the structural formula (1) accounts for 56.8 percent of the content of all Si-H groups, and the molar ratio of allyl groups to Si-H groups is 1: 29.87. placing the allyl-containing liquid polycarbosilane in a 35 ℃ blast oven, and gelling after 15 h. Elemental analysis showed that after 15h incubation at 35 ℃ the oxygen content was 3.35 wt% and before incubation the oxygen content was 1.72 wt%. The ir spectrum showed a significant reduction in the ir absorption peak associated with the unsaturated double bond.
Comparative example 5
With Cl (CH)3O)2SiCH2Cl, vinyl magnesium bromide and the like are taken as raw materials, and according to the preparation method of US7714092B2, the vinyl-containing liquid polycarbosilane is synthesized through Grignard reaction and reduction reaction, and the vinyl-containing liquid polycarbosilane has the number average molecular weight of 1321 and the weight average molecular weight of 4371. The nuclear magnetic spectrum is shown in FIG. 6, and the integral ratio of Si-H groups in the three structural units of structural formula (1), structural formula (2) and structural formula (3) is 2.56 according to nuclear magnetism: 3.39: 1, the content of Si-H groups in the structural formula (1) accounts for 36.8 percent of the content of all Si-H groups, and the molar ratio of vinyl groups to the Si-H groups is 1: 17.1. placing the liquid polycarbosilane with the structure in a 40 ℃ blast oven, and gelling after 37 h. Elemental analysis showed that after incubation at 40 ℃ for 37h, the oxygen content was 2.98 wt.% and before incubation the oxygen content was 1.47 wt.%. The ir spectrum showed a significant reduction in the ir absorption peak associated with the unsaturated double bond.
Comparative example 6
With Cl1.25(CH3O)1.75SiCH2Cl, chloropropene, ethynylmagnesium chloride and the like are taken as raw materials, and according to the preparation method of US7714092B2, liquid polycarbosilane containing ethynyl and allyl is synthesized through Grignard reaction and reduction reaction, the number average molecular weight is 1031, and the weight average molecular weight is 3867. The nuclear magnetic spectrum is shown in FIG. 7, and the integral ratio of Si-H groups in the three structural units of structural formula (1), structural formula (2) and structural formula (3) is 2.82 according to nuclear magnetism: 2.76: 1, the content of Si-H groups in the structural formula (1) was 42.9% of the content of all Si-H groups. The molar ratio of allyl, ethynyl and Si-H groups is 1: 0.38: 41.72. placing the liquid polycarbosilane with the structure in a 35 ℃ blast oven, and gelling after 31 h. Elemental analysis showed that after 31h incubation at 35 ℃ the oxygen content was 3.79 wt% and before incubation the oxygen content was 1.52 wt%. The ir spectrum shows a significant reduction in the ir absorption peak associated with the unsaturated group.
It is clear from comparative examples 1 to 6 that the liquid polycarbosilane of organosilicon polymer containing unsaturated groups and Si-H groups is stable in a nitrogen atmosphere, and the stability is not significantly affected by the presence of neutral water. The crosslinking is easy to be carried out when the film is placed in an air environment at room temperature, and the gelation time is shortened along with the increase of the temperature. However, the increase in the oxygen content before and after gelation at room temperature was not so large and the decrease in the quality was slight, and the decrease in the unsaturated group content was more remarkable. It is presumed that the key element that causes the instability of the film at room temperature is the presence of unsaturated groups and participation in the crosslinking reaction. For the unsaturated groups in the silicone polymer, the mechanism for participating in the crosslinking reaction comprises Si-H addition unsaturated group and self-free radical chain polymerization. In the absence of a catalyst, the Si-H addition double bond is difficult to proceed even when heated at 80 ℃ for 24 hours, demonstrating that the Si-H addition double bond is not easy to proceed at low temperature in the structure of the silicone polymer. Therefore, it is presumed that the most likely crosslinking mechanism is radical chain polymerization of the unsaturated group itself.
Example 1
4-t-butylcatechol (i.e., 4-t-butylcatechol accounted for 0.2% by mass of the allyl-containing liquid polycarbosilane) was added to the allyl-containing liquid polycarbosilane described in comparative example 1 in an amount of 0.20 wt%, and after mixing, the mixture was placed in a 35 ℃ forced air oven and heat-insulated for 10 days, whereby gelation did not occur and fluidity was good. The molecular weight was characterized by gel permeation chromatography and the complex viscosity by rheometer. The number average molecular weight increased from 922 to 1026 and the weight average molecular weight increased from 2490 to 2546. The results of the complex viscosity as a function of shear rate are shown in FIG. 8. In the linear viscoelastic region, the viscosity of example 1 increased from 0.017Pa · S before the incubation to only 0.022Pa · S.
Example 2
4-t-butylcatechol was added to the allyl group-containing liquid polycarbosilane described in comparative example 1 in an amount of 0.20 wt%, and after mixing, the mixture was placed in a 35 ℃ forced air oven and kept at a temperature for 20 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography and the complex viscosity by rheometer. The number average molecular weight increases from 922 to 1091 and the weight average molecular weight increases from 2490 to 2742. The results of the complex viscosity as a function of shear rate are shown in FIG. 8. In the linear viscoelastic region, the viscosity of example 2 increased from 0.017Pa · S to 0.024Pa · S.
Example 3
4-t-butylcatechol was added to the allyl group-containing liquid polycarbosilane described in comparative example 1 in an amount of 0.20 wt%, and after mixing, the mixture was placed in a 35 ℃ forced air oven and heat-preserved for 30 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography and the complex viscosity by rheometer. The number average molecular weight increases from 922 to 1138 and the weight average molecular weight increases from 2490 to 2778. The results of the complex viscosity as a function of shear rate are shown in FIG. 8. In the linear viscoelastic region, the viscosity of example 3 increased from 0.017Pa · S to 0.025Pa · S.
Example 4
4-t-butylcatechol was added to the allyl group-containing liquid polycarbosilane described in comparative example 1 in an amount of 0.20 wt%, and after mixing, the mixture was placed in a 35 ℃ forced air oven and heat-preserved for 60 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography and the complex viscosity by rheometer. The number average molecular weight increased from 922 to 1138 and the weight average molecular weight increased from 2490 to 2999. The results of the complex viscosity as a function of shear rate are shown in FIG. 8. In the linear viscoelastic region, the viscosity of example 4 increased from 0.017Pa · S to 0.028Pa · S. The silicon carbide ceramic is cracked to 1600 ℃ under the argon atmosphere, and the X-ray diffraction peak of the silicon carbide ceramic is shown in figure 9, which shows that the organic silicon composition can be converted into the crystalline silicon carbide ceramic through high-temperature treatment.
Example 5
4-tert-butylcatechol was added to the allyl group-containing liquid polycarbosilane described in comparative example 1 in an amount of 0.5 wt%, and the mixture was placed in a 35 ℃ forced air oven and kept at a temperature of 60 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography, with the number average molecular weight increasing from 922 to 1104 and the weight average molecular weight increasing from 2490 to 2658.
Example 6
4-t-butylcatechol was added to the allyl group-containing liquid polycarbosilane described in comparative example 1 in an amount of 1.0 wt%, and the mixture was held in a forced air oven at 40 ℃ for 60 days without gelling and was flowable. The molecular weight was characterized by gel permeation chromatography, with the number average molecular weight increasing from 922 to 1352 and the weight average molecular weight increasing from 2490 to 5729.
Example 7
4-t-butylcatechol was added to the allyl group-containing liquid polycarbosilane described in comparative example 4 in an amount of 0.25 wt%, and the mixture was held in a 35 ℃ forced air oven for 60 days without gelling and was flowable. The molecular weight was characterized by gel permeation chromatography, with the number average molecular weight increasing from 1462 to 1526 and the weight average molecular weight increasing from 9642 to 13824.
Example 8
4-propylcatechol was added to the vinyl group-containing liquid polycarbosilane described in comparative example 5 in an amount of 0.5 wt%, and the mixture was held in a 40 ℃ forced air oven for 30 days without gelling and with good fluidity. The molecular weight was characterized by gel permeation chromatography, with the number average molecular weight increasing from 1321 to 1374 and the weight average molecular weight increasing from 4371 to 4865.
Example 9
To the liquid polycarbosilane containing ethynyl and allyl groups described in comparative example 6 was added 1,3, 5-trinitrobenzene at a content of 0.25 wt%, and the mixture was placed in a 35 ℃ forced air oven and kept at a temperature for 60 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increased from 1031 to 1182, and the weight average molecular weight increased from 3867 to 4739.
Example 10
2, 5-di-tert-amyl-1, 4-benzoquinone with the content of 0.2 wt% is added into the allyl-containing liquid polycarbosilane in the comparative example 1, and the mixture is placed in a 35 ℃ blast oven and is kept warm for 60 days, so that gelation does not occur, and the fluidity is good. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increased from 922 to 1249 and the weight average molecular weight increased from 2490 to 3318.
Example 11
4-tert-butylcatechol in an amount of 0.06 wt% and 2, 5-di-tert-amyl-1, 4-benzoquinone in an amount of 0.14 wt% were added to the liquid allyl-containing polycarbosilane described in comparative example 1, and the mixture was placed in a 35 ℃ forced air oven and kept at the temperature for 60 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increased from 922 to 1101 and the weight average molecular weight increased from 2490 to 3006.
Example 12
4-t-butylcatechol in an amount of 0.1 wt% and 2, 5-di-t-amyl-1, 4-benzoquinone in an amount of 0.1 wt% were added to the liquid allyl-containing polycarbosilane described in comparative example 1, and the mixture was placed in a 35 ℃ forced air oven and allowed to stand for 60 days without gelling and with good fluidity. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increased from 922 to 1036 and the weight average molecular weight increased from 2490 to 2647.
Example 13
4-t-butylcatechol in an amount of 0.13 wt% and 2, 5-di-t-amyl-1, 4-benzoquinone in an amount of 0.07 wt% were added to the liquid allyl-containing polycarbosilane described in comparative example 1, and the mixture was placed in a 35 ℃ forced air oven and allowed to stand for 60 days without gelling and with good fluidity. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increased from 922 to 1023 and the weight average molecular weight increased from 2490 to 2590.
Example 14
4-t-butylcatechol in an amount of 0.15 wt% and 2, 5-di-t-amyl-1, 4-benzoquinone in an amount of 0.05 wt% were added to the liquid allyl-containing polycarbosilane described in comparative example 1, and the mixture was placed in a 35 ℃ forced air oven and kept at the temperature for 60 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increases from 922 to 1065 and the weight average molecular weight increases from 2490 to 2751.
Example 15
4-t-butylcatechol in an amount of 0.17 wt% and 2, 5-di-t-amyl-1, 4-benzoquinone in an amount of 0.03 wt% were added to the liquid allyl-containing polycarbosilane described in comparative example 1, and the mixture was placed in a 35 ℃ forced air oven and allowed to stand for 60 days without gelling and with good fluidity. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increased from 922 to 1136 and the weight average molecular weight increased from 2490 to 2993.
As proved by the embodiment 4 and the embodiments 10-15, when the adopted stabilizer is a phenolic compound and a quinone compound, the mass ratio of the phenolic compound to the quinone compound is (1-3): 1, the silicone composition has more excellent stability.
Example 16
4, 4' -diaminodiphenyl ether was added to the allyl-containing liquid polycarbosilane described in comparative example 1 in an amount of 0.2 wt%, and the mixture was placed in a 35 ℃ forced air oven and kept warm for 30 days without gelation and with good fluidity. The molecular weight was characterized by gel permeation chromatography. The number average molecular weight increased from 922 to 1374 and the weight average molecular weight increased from 2490 to 3862. The silicon carbide is cracked to 1600 ℃ in an argon atmosphere, and the result of X-ray diffraction shows that the silicon carbide can be converted into crystalline silicon carbide.
Example 17
The silicon carbide fiber woven tube was placed in a measuring cylinder, the silicone composition described in example 1 was added, and vacuum impregnation was performed. After the removal, the silicone composition adhering to the surface was wiped off. Putting the mixture into a pyrolysis furnace, and heating the mixture in a nitrogen atmosphere according to the following procedures: raising the temperature to 1200 ℃ at a speed of 10 ℃/min, and keeping the temperature for 1h at 200 ℃ and 1200 ℃ respectively. And repeating the vacuum impregnation and cracking processes for 9 times to realize the densification of the silicon carbide fiber reinforced silicon carbide composite pipe fitting. The silicon carbide fiber content in the resulting composite was calculated to be 55.3 wt%. The profile and internal profile of the resulting tube are shown in figure 10.
Example 18
2g of silicon carbide whiskers were added to 20mL of an n-heptane solution of the silicone composition described in example 11 (the silicone composition content was 20 wt%). Mechanically stirred at high speed for 1 hour to disperse the SiC whiskers. After being stirred evenly, the mixture is poured into a mould and is filtered by suction to obtain a cylindrical block. Then putting the mixture into a pyrolysis furnace, heating the mixture to 1500 ℃ at the speed of 10 ℃/min in an argon atmosphere, and preserving the heat for 1 hour, wherein the heat is preserved for 1 hour at the temperature of 200 ℃. The density obtained was 0.36g/cm3The porous silicon carbide of (2). The appearance and the scanning electron micrograph of the silicon carbide crystal whisker are shown in fig. 11, and the silicon carbide crystal whisker is bonded with each other through the liquid polycarbosilane after cracking to form a block. The compressive stress-strain curve is shown in fig. 12, and shows superior mechanical strength.
The silicon composition can be applied to the preparation of silicon carbide materials such as silicon carbide ceramic matrix composites and porous silicon carbide as can be proved by the examples 17 and 18.
The performance tests in the comparative examples and examples above were carried out using the following instruments:
infrared spectrum: testing by adopting a U.S. Thermo Nicolet 6700 Fourier transform infrared spectrometer;
nuclear magnetism: testing by adopting a Bruker Avance III nuclear magnetic resonance instrument of Germany Bruker company;
molecular weight: testing by using HLC-8320GPC gel permeation chromatograph of Japan TOSOH company;
oxygen content: testing by adopting an EMGA-620 type oxygen nitrogen analyzer of HORIBA company of Japan;
thermal weight loss: adopting a thermogravimetric analyzer for testing TG-DTA 6300 produced by Japanese fine work;
rheological behavior: testing by adopting an Austria Physica MCR 301 rheometer;
x-ray diffraction: the test is carried out by adopting a Bruker D8 advanced polycrystal X-ray diffractometer of Germany Bruker company;
scanning electron microscope: testing by using a Japanese Hitachi S-4800 type field emission scanning electron microscope;
compressive stress-strain curve: the test was carried out using an Instron model5567 Universal Material testing machine from Instron, USA.
Finally, it should be noted that the specific examples described herein are merely illustrative of the spirit of the invention and do not limit the embodiments of the invention. Those skilled in the art may now make numerous modifications of, supplement, or substitute for the specific embodiments described, all of which are not necessary or desirable to describe herein. While the invention has been described with respect to specific embodiments, it will be appreciated that various changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims.
Claims (13)
1. A silicone composition comprising a silicone polymer and a stabilizer; the organic silicon polymer is polycarbosilane containing unsaturated groups, and the stabilizer is a compound capable of consuming free radicals or reducing the activity of the free radicals.
2. The silicone composition according to claim 1, wherein the silicone polymer has a structural unit represented by the following formula (1), formula (2), formula (3), and formula (4):
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10Independently of each other, is selected from one of C1-C6 alkyl and unsaturated group, but R1、R2、R3、R4、R5、R6、R7、R8、R9、R10At least one of which is selected from unsaturated groups and whichThe structural unit is present in the silicone polymer structure.
3. The silicone composition according to claim 1 or 2, characterized in that the unsaturated group is a C ═ C and/or C ≡ C-containing unsaturated group.
4. The silicone composition according to claim 3, wherein the C ≡ C and/or C ≡ C-containing unsaturated group is a vinyl group, an ethynyl group, a propargyl group, or an allyl group.
5. The organosilicon composition of claim 1, wherein the stabilizer is selected from one or more of aromatic amine compounds, phenolic compounds, quinone compounds, nitro compounds, and nitroso compounds.
6. The silicone composition according to claim 1 or 5, characterized in that the stabilizer is a phenolic compound.
7. The silicone composition according to claim 6, wherein the phenolic compound is a polyhydric phenol having an alkyl substituent.
8. The organosilicon composition according to claim 1, wherein the stabilizer is a phenolic compound and a quinone compound in a mass ratio (1-3): 1, mixing the mixture.
9. The silicone composition according to claim 8, wherein the quinone compound is a quinone compound having an alkyl substituent.
10. The silicone composition according to claim 1, characterized in that 0% < mass of stabilizer/mass of silicone polymer ≦ 1%.
11. The silicone composition according to claim 1, characterized in that 0% < mass of stabilizer/mass of silicone polymer < 0.2%.
12. The silicone composition of claim 1, further comprising a ceramic filler or a metal compound filler.
13. Use of a silicone composition according to claim 1 in the preparation of a silicon carbide ceramic, wherein the silicone composition is converted to a silicon carbide ceramic by heating.
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