CN102604108A - Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof - Google Patents
Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof Download PDFInfo
- Publication number
- CN102604108A CN102604108A CN2012100688718A CN201210068871A CN102604108A CN 102604108 A CN102604108 A CN 102604108A CN 2012100688718 A CN2012100688718 A CN 2012100688718A CN 201210068871 A CN201210068871 A CN 201210068871A CN 102604108 A CN102604108 A CN 102604108A
- Authority
- CN
- China
- Prior art keywords
- dichlorosilane
- carbon atoms
- total number
- substituent
- chlorosilane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicon Polymers (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses an organic silicon binding agent and a special silicon-boron-carbon-nitrogen polymer thereof. The silicon-boron-carbon-nitrogen polymer provided by the invention is formed by mixing two types of chlorsilane and chloroborane according to a certain mixture ratio, wherein at least one of the two types of chlorsilane is the chlorsilane with a silicon-olefin structure, and co-ammonolysis or aminolysis is performed for completion. The novel silicon-boron-carbon-nitrogen polymer is developed by the invention, and a ceramic organic silicon binding agent with resistance to ultra-high temperature can be prepared by taking the two polymers as base adhesives. The binding agent disclosed by the invention can be cured at lower temperature and has good toughness after curing; and as the binding agent, the temperature resistance is high, heat stability, mechanical properties and binding performance are good, and the equivalent shearing strength can be still kept at the temperature of 1500 DEG C.
Description
Technical field
The present invention relates to a kind of organosilicon sticker and special-purpose Si-B-C-N polymkeric substance thereof.
Background technology
At present; The superhigh temperature resistant sticker comprises mineral binder bond, silicone resin, modified phenolic etc.; Mineral binder bond be made up of inorganic salt, mineral acid, inorganic base metal and MOX, metal hydroxides etc. one type is sticker quite widely; Resistance to elevated temperatures is extremely excellent, can in 180～2900 ℃ of scopes, be widely used.Have the performance of many excellences for modified phenolic class sticker, be widely used in fields such as Aeronautics and Astronautics.The molecular backbone chain structure of silicone resin is made up of the very high siliconoxygen bond of bond energy, and is high more a lot of than the molecular structure thermotolerance of carbochain, is the principal constituent of good heat-resistant adhesive.
But also there are some problems in these stickers, and are the highest like the mineral binder bond heat resisting temperature, but its fragility is bigger, poor thermal shock resistance, and the corrosion certain to material production.Silicone resin, modified phenolic etc. belong to thermosetting resin, need solidify at comparatively high temps, and it are very big to solidify the back material fragility, and adhesive property is relatively poor under the high temperature.
In recent years; Along with both at home and abroad with ceramic precursor polymer application carrying out in adhesive research work; Just for breaking through the inorganic and inherent defective of organic adhesion agent of tradition own; Good novel of development over-all properties the superhigh temperature resistant characteristic of organic adhesion agent favorable manufacturability, environmental stability and inorganic adhesive combined, for can potteryization high-temperature resistance adhesive provide possible.Ceramic precursor is the performance that is organic materials under one type of low temperature, is converted into the polymkeric substance of stupalith through heat, is with a wide range of applications in fields such as Aeronautics and Astronautics, weapons, naval vessels.And cause extensive concern owing to the excellent properties of precursor itself based on the sticker of ceramic precursor.Particularly has prior application prospect owing to hot strength, high-modulus and the excellent high-temperature oxidation and the high-temperature creep resistance of the excellence of Si, B, C, the many units of N pottery self based on the vitrified bond of elements such as Si, B, C, N.
Summary of the invention
The purpose of this invention is to provide a kind of organosilicon caking agent and special-purpose Si-B-C-N polymkeric substance thereof.
The method for preparing the Si-B-C-N polymkeric substance provided by the invention; Comprise the steps: in inert atmosphere, chloroborane, ammonia source compound, solvent and at least two kinds of chlorosilanes are mixed react, after reaction system is alkalescence, stop to feed said ammonia source compound; Be warming up to room temperature; Under inert atmosphere protection,, vacuumize behind the merging filtrate to remove and desolvate, obtain said Si-B-C-N polymkeric substance with said solvent filter reaction system.
Aforesaid method is with two kinds of chlorosilanes and the common ammonia of chloroborane separates or aminolysis makes; In the said chlorosilane, have at least a kind of for containing the chlorosilane of silicon-alkene structures; In the said chlorosilane that contains silicon-alkene structures, said silicon-alkene structures be the total number of carbon atoms be 2-4 alkenyl or; Said containing in the alkenyl that substituent the total number of carbon atoms is 2-4, said substituting group is selected from least a in methyl, ethyl and the chlorine;
The preferred RSiCl of said chlorosilane
3, R
2SiCl
2And R
3Among the SiCl at least two kinds; Wherein, said R be hydrogen, the total number of carbon atoms be 1-6 alkyl, naphthenic base that the total number of carbon atoms is 3-6, contain naphthenic base that substituent the total number of carbon atoms is 3-6, alkenyl that the total number of carbon atoms is 2-4, aryl that the total number of carbon atoms is 6-10, contain substituent the total number of carbon atoms and be the alkenyl of 2-4 and contain at least a in the aryl that substituent the total number of carbon atoms is 6-10; Said contain naphthenic base that substituent the total number of carbon atoms is 3-6, contain substituent the total number of carbon atoms be the alkenyl of 2-4 and contain in the aryl that substituent the total number of carbon atoms is 6-10 that said substituting group is selected from least a in methyl, ethyl and the chlorine;
Said R be hydrogen, the total number of carbon atoms be 1-6 alkyl, naphthenic base that the total number of carbon atoms is 3-6, contain naphthenic base that substituent the total number of carbon atoms is 3-6, alkenyl that the total number of carbon atoms is 2-4, aryl that the total number of carbon atoms is 6-10, contain substituent the total number of carbon atoms and be the alkenyl of 2-4 and contain at least two kinds in the aryl that substituent the total number of carbon atoms is 6-10; Said contain naphthenic base that substituent the total number of carbon atoms is 3-6, contain substituent the total number of carbon atoms be the alkenyl of 2-4 and contain in the aryl that substituent the total number of carbon atoms is 6-10 that said substituting group is selected from least a in methyl, ethyl and the chlorine;
Said chlorosilane specifically is selected from the methyl ethylene dichlorosilane; The methylpropenyl dichlorosilane; Vinyl toluene base dichlorosilane; The ethyl vinyl dichlorosilane; The divinyl dichlorosilane; To the styryl dichlorosilane; Vinyl trichloro silane; The styryl trichlorosilane; The dimethyl-vinyl chlorosilane; The methylethyl vinyl chlorosilane; The phenyl vinyl dichlorosilane; The methyl phenyl vinyl chlorosilane; Dichlorosilane; Dimethyl dichlorosilane (DMCS); Dimethyldichlorosilane(DMCS); Diethyl dichlorosilane; Ethyl dichlorosilane; The n-propyl dichlorosilane; The dipropyl dichlorosilane; Trichlorosilane; METHYL TRICHLORO SILANE; Ethyl trichlorosilane; Phenyl-trichloro-silicane; The normal-butyl dichlorosilane; The isobutyl-dichlorosilane; The isopentyl dichlorosilane; The benzyl dichlorosilane; The naphthyl dichlorosilane; The propenyl dichlorosilane; Diphenyl dichlorosilane; Diphenyl dichlorosilane; The methylethyl dichlorosilane; The methyl ethylene dichlorosilane; Dichloromethyl phenylsilane; The dibenzyl dichlorosilane; The rubigan dichlorosilane; The n-hexyl dichlorosilane; The cyclohexyl dichlorosilane; The dicyclohexyl chlorosilane; The diisobutyl dichlorosilane; The p-methylphenyl dichlorosilane; Two pairs of phenyl chlorosilanes; To at least two kinds in styryl dichlorosilane and the ethynyl dichlorosilane;
Said chloroborane is selected from R
2BCl, RBCl
2, BCl
3, R
2NBCl
2, RN
2BCl, R
2B
3N
3Cl, RB
3N
3Cl
2And B
3N
3Cl
3In at least a; Wherein, R be hydrogen, the total number of carbon atoms be 1-6 alkyl, naphthenic base that the total number of carbon atoms is 3-6, contain naphthenic base that substituent the total number of carbon atoms is 3-6, alkenyl that the total number of carbon atoms is 2-4, aryl that the total number of carbon atoms is 6-10, contain substituent the total number of carbon atoms and be the alkenyl of 2-4 and contain at least a in the aryl that substituent the total number of carbon atoms is 6-10; Said contain naphthenic base that substituent the total number of carbon atoms is 3-6, contain substituent the total number of carbon atoms be the alkenyl of 2-4 and contain in the aryl that substituent the total number of carbon atoms is 6-10 that said substituting group is selected from least a in methyl, ethyl and the chlorine; Said chloroborane is selected from least a in a chloroborane, two chloroboranes, three chloroboranes, methyl dichloro borine, the substituted chloroborane of amido, the substituted borazine of chlorine and the trichlorine borazine;
Said ammonia source compound is selected from least a in ammonia and the organic amine; Wherein, said organic amine is selected from least a in methylamine, ethamine, quadrol, propylamine, aniline and the Ursol D;
Said solvent is selected from least a in alkane that the total number of carbon atoms is 6-10, aromatic hydrocarbons that the total number of carbon atoms is 6-8, ether that the total number of carbon atoms is 4-8 and the furans, specifically is selected from least a in hexane, toluene, YLENE, ether, the THF.
The molar ratio of said chlorosilane and said chloroborane is 1-20: 1-20, preferred 1-5: 1-5; The consumption of said solvent is said chloroborane and chlorosilane gross weight 1～10 times, preferred 2～4 times.The mole dosage that feeds intake of chlorosilane is the summation of used various chlorosilane mole dosage here.
In the said reactions step, temperature is-20～-10 ℃, preferred-15～-12 ℃.
The Si-B-C-N polymkeric substance for preparing according to the method described above also belongs to protection scope of the present invention.Wherein, the number-average molecular weight of said Si-B-C-N polymkeric substance is 500-3000, preferred 600-1500; 25 ℃ viscosity is 800-80000cp, preferred 900-5000cp.
Organosilicon sticker provided by the invention comprises each component of following weight part:
Above-mentioned organosilicon caking agent also can only be made up of said components.Said organosilicon caking agent also comprises at least a in following each component: Si
3N
4, B
4C, MgO, ZrO
2, ZrC, TiN, AlN, Si, B, TiB
2, BN, Al
2O
3And superoxide;
The weight part of above-mentioned each component is respectively:
Said Si
3N
4, B
4C, MgO, ZrO
2, ZrC, TiN, AlN, Si, B, TiB
2, BN and Al
2O
3Weight part all be not 0;
Said superoxide is selected from Di Cumyl Peroxide 99, at least a in two (2,4 dichloro benzene formyl) superoxide.
The method of the said organosilicon sticker of preparation provided by the invention comprises the steps: obtaining said organosilicon caking agent after aforementioned each component mixing, the degassing and the curing.
In the said degassing step of aforesaid method, pressure is-0.05～-0.1MPa, the time is 5-10 minute;
In the said curing schedule, temperature is 150～200 ℃, preferred 160～180 ℃, and 1～3 hour time, preferred 2 hours.
In addition, contain the caking agent and the application of this organosilicon caking agent in the preparation caking agent of the organosilicon caking agent that the invention described above provides, also belong to protection scope of the present invention.
The present invention is based on the Si-B-C-N polymkeric substance is basic glue, and composite high temperature resistant filler, prepares a kind of superhigh temperature resistant organosilicon sticker that can potteryization.Same resol, polyimide are compared, and sticker of the present invention can solidify at lesser temps, and have good toughness after solidifying; This sticker has excellent heat resistance in addition, and excellent thermostability, good mechanical performance and adhesive property still have very high shearing resistance at 1500 ℃, and can be used under oxidation, reduction, inertia and the vacuum atmosphere.Compare with mineral binder bond, the sticker that this can potteryization removes has excellent temperature tolerance, also has good toughness, has important use and is worth.
Description of drawings
Fig. 1 is the infrared spectrum of embodiment 1 synthetic Si-B-C-N polymkeric substance.
Fig. 2 is the silicon spectrum of embodiment 1 synthetic polymkeric substance.
Fig. 3 is the boron spectrum of embodiment 1 synthetic polymkeric substance.
Fig. 4 is the thermogravimetric curve under the nitrogen atmosphere after the embodiment 1 synthetic polymer cure.
Fig. 5 is the aerial thermogravimetric curves of embodiment 8 preparation gained organosilicon stickers.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but the present invention is not limited to following examples.Said method is ordinary method if no special instructions.Said starting material all can get from open commercial sources if no special instructions.The consumption umber of said component is parts by weight if no special instructions; The said proportioning of each component if no special instructions, is parts by weight among the said embodiment 8-17.
Embodiment 1
(1) will vacuumize repeatedly with the reactor drum of the 250ml of magnetic agitation, inflated with nitrogen three times then adds organic solvent ether (volume ratio of solvent and reactant is 3: 1), while stirring temperature of reactor is reduced to-15 ℃ then; (2) get methyl ethylene dichlorosilane 0.2mol (28.2g) with syringe; Methyl hydrogen dichlorosilane 0.1mol (13.6g); Boron trichloride 0.15mol (11.8g) successively adds in the reactor drum, and chlorosilane and trichlorine borazine mol ratio are after stirring at 2: 1, to feed industrial ammonia then; Producing a large amount of white precipitates in the system rapidly, is alkalescence up to system pH.(3) rise to room temperature naturally when system temperature, under nitrogen atmosphere, begin then to filter, with ether solvent repetitive scrubbing filter cake at least 3 times, merging filtrate.In room temperature, vacuum condition removes down and desolvates, and obtains water white liquid-state silicon boron carbon nitrogen polymer with the filtrating that obtains.Synthetic yield is 80%, adopts GPC to measure the molecular weight of polymkeric substance, and the number-average molecular weight of polymkeric substance is 853, and viscosity is 1500cp.
Its ir spectra, as shown in Figure 1.
By finding out among Fig. 1, there is Si-H in this polymkeric substance, Si-N, B-N, Si-H, the absorption peak of groups such as Si-CH=CH2.
Its nuclear magnetic spectrogram, like Fig. 2, shown in 3, Fig. 2 is the silicon spectrum of polymkeric substance, as can be seen from the figure-22ppm belongs to SiN
3C-structure ,-17ppm belongs to Si-CH=CH
2And Si-CH
3The peak between 2.4～3ppm, be two peak structure.Fig. 3 is the boron spectrum of this polymkeric substance, and single broad peak is only arranged, and corresponding peak belongs to BN
3Structure.
Fig. 4 provides the thermogravimetric curve under the nitrogen atmosphere after this polymer cure, as can be seen from the figure, the polymkeric substance weightlessness after the curing mainly between 400～700 ℃, 1100 ℃ residual heavy up to 77%.
Embodiment 2
Reactor drum with the 250ml that is with magnetic agitation vacuumizes repeatedly, and inflated with nitrogen three times then adds organic solvent YLENE (volume ratio of solvent and reactant is 10: 1), while stirring temperature of reactor is reduced to-20 ℃ then; (2) get ethylethylene dichlorosilane 0.2mol (31g) with syringe, methyl hydrogen dichlorosilane 0.1mol (11.5g), vinyl trichloro silane 0.1mol (16.2g); Trichlorine borazine 0.02mol (3.6g) successively adds in the reactor drum, and chlorosilane and trichlorine borazine mol ratio are 20: 1; After stirring; Feeding industrial methylamine then, produce a large amount of white precipitates in the system rapidly, is alkalescence up to system pH.(3) rise to room temperature naturally when system temperature, under nitrogen atmosphere, begin then to filter, with xylene solvent repetitive scrubbing filter cake at least 3 times, merging filtrate.In room temperature, vacuum condition removes down and desolvates, and obtains water white liquid-state silicon boron carbon nitrogen polymer with the filtrating that obtains.Synthetic yield is 73%, adopts GPC to measure the molecular weight of polymkeric substance, and the number-average molecular weight of polymkeric substance is 1230, and viscosity is 2300cp.
Embodiment 3
Reactor drum with the 250ml that is with magnetic agitation vacuumizes repeatedly, and inflated with nitrogen three times then adds organic solvent tetrahydrofuran (volume ratio of solvent and reactant is 1: 1), while stirring temperature of reactor is reduced to-20 ℃ then; (2) get allyldichlorosilane 0.1mol (31g) with syringe;, trichlorine borazine 0.02mol (3.6g) successively adds in the reactor drum, and chlorosilane and trichlorine borazine mol ratio are 1: 20; After stirring; Feeding industrial methylamine then, produce a large amount of white precipitates in the system rapidly, is alkalescence up to system pH.(3) rise to room temperature naturally when system temperature, under nitrogen atmosphere, begin then to filter, with xylene solvent repetitive scrubbing filter cake at least 3 times, merging filtrate.In room temperature, vacuum condition removes down and desolvates, and obtains water white liquid-state silicon boron carbon nitrogen polymer with the filtrating that obtains.Synthetic yield is 76%, adopts GPC to measure the molecular weight of polymkeric substance, and the number-average molecular weight of polymkeric substance is 1650, and viscosity is 7000cp.
Embodiment 4
(1) with (1) among the embodiment 1, toluene is solvent (volume ratio of solvent and reactant is 4: 1); (2) get methyl ethylene dichlorosilane 0.2mol (28.2g) with syringe, trichlorosilane alkane 0.1mol (13.6g), two chloroborane 0.15mol (12.4g) successively add in the reactor drum; Chlorosilane and trichlorine borazine mol ratio are 2: 1; After stirring, feed industrial ammonia then, produce a large amount of white precipitates in the system rapidly; Up to system pH is alkalescence, stops to feed ammonia.(3) rise to room temperature naturally when system temperature, under nitrogen atmosphere, begin then to filter, with toluene solvant repetitive scrubbing filter cake at least 3 times, merging filtrate.In room temperature, vacuum condition removes down and desolvates, and obtains water white liquid-state silicon boron carbon nitrogen polymer with the filtrating that obtains.Synthetic yield is 83%, adopts GPC to measure the molecular weight of polymkeric substance, and the number-average molecular weight of polymkeric substance is 780, and viscosity is 1200cp.
Embodiment 5
(1) with (1) among the embodiment 1, THF is solvent (volume ratio of solvent and reactant is 5: 1); (2) get vinyl trichloro silane 0.3mol (48.4g) with syringe; Methyl hydrogen dichlorosilane 0.3mol (34.5g); Trichlorine borazine 0.2mol (36.3g) successively adds in the reactor drum, and chlorosilane and trichlorine borazine mol ratio are after stirring at 3: 1, to feed industrial ammonia then; Producing a large amount of white precipitates in the system rapidly, is alkalescence up to system pH.(3) rise to room temperature naturally when system temperature, under nitrogen atmosphere, begin then to filter, with tetrahydrofuran solvent repetitive scrubbing filter cake at least 3 times, merging filtrate.In room temperature, vacuum condition removes down and desolvates, and obtains water white liquid-state silicon boron carbon nitrogen polymer with the filtrating that obtains.Synthetic yield is 79%, adopts GPC to measure the molecular weight of polymkeric substance, and the number-average molecular weight of polymkeric substance is 840, and viscosity is 1300cp.
Embodiment 6
(1) with (1) among the embodiment 1, use sherwood oil to be solvent, the volume ratio of solvent and reactant is 2: 1; (2) get styryl dichlorosilane 0.1mol (20.3g) with syringe; METHYL TRICHLORO SILANE 0.2mol (29.9g), methyl dichloro borine 0.3mol (29.1g) successively adds in the reactor drum, and chlorosilane and trichlorine borazine mol ratio are 1: 1; After stirring; Feeding methylamine then, produce a large amount of white precipitates in the system rapidly, is alkalescence up to system pH.(3) rise to room temperature naturally when system temperature, under nitrogen atmosphere, begin then to filter, with petroleum ether solvent repetitive scrubbing filter cake at least 3 times, merging filtrate.In room temperature, vacuum condition removes down and desolvates, and obtains water white liquid-state silicon boron carbon nitrogen polymer with the filtrating that obtains.Synthetic yield is 85%, and the number-average molecular weight of polymkeric substance is 910, and viscosity is 11200cp.
Embodiment 7
(1), use THF to be solvent with (1) among the embodiment 1; (2) get methylpropenyl dichlorosilane 0.2mol (25.4g) with syringe; Dichloromethyl phenylsilane 0.2mol (38.2g), methyl dichloro borazine 0.2mol (32.2g) successively adds in the reactor drum, and chlorosilane and trichlorine borazine mol ratio are 2: 1; After stirring; Feeding ethamine then, produce a large amount of white precipitates in the system rapidly, is alkalescence up to system pH.(3) rise to room temperature naturally when system temperature, under nitrogen atmosphere, begin then to filter, with tetrahydrofuran solvent repetitive scrubbing filter cake, merging filtrate.In room temperature, vacuum condition removes down and desolvates, and obtains water white liquid-state silicon boron carbon nitrogen polymer with the filtrating that obtains.Synthetic yield is 81%, and the number-average molecular weight of polymkeric substance is 870, and viscosity is 8500cp.
Second section can potteryization superhigh temperature resistant sticker preparation
The curing process of this superhigh temperature resistant organosilicon sticker:
In 100 parts of Si-B-C-N polymkeric substance, add a certain amount of auxiliary packing; Utilize after mixing well water pump-0.05～-the 0.1MPa vacuum condition under the degassing 5～10 minutes; Solidify back (150～200 ℃ of solidification values (preferred 160～180 ℃); 1～3 hour set time (preferred 2 hours)), promptly can be used as superhigh temperature resistant organosilicon caking agent or sealing agent uses.
The Si-B-C-N polymkeric substance; It at high temperature transforms the Si-B-C-N ceramic of formation, and its thermostability can reach 2000 ℃, is a kind of very excellent high temperature material; Excellent properties just because of precursor itself; Composite more corresponding high temperature resistant filler can prepare can potteryization the superhigh temperature resistant caking agent, so organosilicon caking agent of the present invention has excellent temperature tolerance, but heatproof is more than 1500 ℃.
In beaker, add 100 parts of Si-B-C-N polymkeric substance of synthetic (embodiment 1 is synthetic), 2 parts of antistructurizing agent hexamethyldisilazanes or pregnancy basic ring three silazane, 30 parts of SiO
2, 10 parts of ZrB
2, 5 parts of SiC, 15 parts of Al
2O
3, 10 parts of Ti, 5 parts of Si, 15 parts of TiC, 5Fe
2O
3, adding 1 part Di Cumyl Peroxide 99, abundant mixing as the sticker of metal or graphite, stupalith, after the curing, is measured adhesive property, cuts intensity for measuring to draw between metallic substance, measures compression shear strength for pottery or matrix material.
As shown in table 1, provide sticker the shearing resistance room temperature and air atmosphere under high-temperature heat treatment after of this Si-B-C-N polymkeric substance as graphite material, table 2 provides the room temperature cohesive strength of Si-B-C-N polymer bonding agent to metal, stupalith.
Table 1, the organosilicon caking agent mechanical property of thermal treatment after 10 minutes under room temperature and differing temps air atmosphere
| Thermal treatment temp (℃) | |
800 | 1200 | 1300 | 1500℃ |
| Shearing resistance (MPa) | 7.40 | 6.39 | 7.28 | 7.39 | 14.4 |
Table 2, organosilicon caking agent are to the cohesive strength of metal, stupalith
Can know that by table this sticker all has extraordinary adhesive property for metal, pottery and matrix material, has extensive applicability.
Embodiment 8
The proportioning of each component of sticker that provides according to table 3; Add 1 part of Di Cumyl Peroxide 99, mixing, the degassing (pressure is-0.05MPa that the time is 5 minutes) under vacuum condition, 160 ℃ of curing are after 2 hours; With its sticker as graphite substrate material; Process 5 groups of bonding piece, measure room temperature, high-temperature behavior respectively, the result is as shown in table 4.
The composition of table 3 sticker and proportioning
Wherein, MM
NBe hexamethyldisilazane
The Si-B-C-N polymkeric substance is first part synthetic (embodiment 1 is synthetic).
The shearing resistance of table 4 sticker under room temperature and 1500 ℃
Can know that by table this sticker has extraordinary cohesiveness for graphite substrate material, particularly under 1500 ℃ high temperature, because the reaction between sticker and graphite, adhesive property is further enhanced.
Fig. 5 prepares the aerial thermogravimetric curve of gained organosilicon sticker for this embodiment.As can be seen from the figure, from room temperature～650 ℃, along with the rising of temperature, sticker weightlessness progressively increases, and maximum weightlessness is 4.3%, and continues elevated temperature, because the oxidation of filler causes the weight of sticker progressively to increase.
Embodiment 9
The proportioning of each component of sticker that provides according to table 5; Add a two (2; The 4-dichloro-benzoyl) superoxide mixing, the degassing (pressure is-0.1MPa that the time is 10 minutes), 180 ℃ of curing are after 2 hours, with its sticker as graphite substrate material; Process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is as shown in table 6.
The composition of table 5 sticker and proportioning
MM wherein
NBe hexamethyldisilazane.
The Si-B-C-N polymkeric substance is first part synthetic (embodiment 1 is synthetic).
The shearing resistance of table 6 sticker under room temperature and 1500 ℃
Can know under the high temperature of room temperature and 1500 ℃, still to have extraordinary adhesive property for forms the sticker that disposes with proportioning by table 5 by table.
The proportioning of each component of sticker that provides according to table 7; Add 1 part of Di Cumyl Peroxide 99; Mixing, the degassing (pressure is-0.08MPa that the time is 8 minutes), 200 ℃ of curing are after 3 hours, with its sticker as the silicon nitride ceramics body material; Process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is as shown in table 8.
The composition of table 7 sticker and proportioning
MM wherein
NBe hexamethyldisilazane.
The Si-B-C-N polymkeric substance is first part synthetic (embodiment 4 is synthetic).
The shearing resistance of table 8 sticker under room temperature and 1500 ℃
Can know that by table for the silicon nitride ceramics body material, sticker has adhesive property preferably equally, at high temperature not have between sticker and silicon nitride to produce stronger bonding force, decrease so the shearing resistance under 1500 ℃ is compared with room temperature.
Embodiment 11
The proportioning of each component of sticker that provides according to table 9; Add a two (2,4 dichloro benzene formyl) superoxide, (pressure is-0.05MPa for mixing, the degassing; Time is 10 minutes), 160 ℃ solidify after 2 hours; With its sticker as silicon carbide ceramics matrix material, process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is as shown in table 10.
The composition of table 9 sticker and proportioning
MM wherein
NBe hexamethyldisilazane.
The Si-B-C-N polymkeric substance is first part synthetic (embodiment 5 is synthetic).
The shearing resistance of table 10 sticker under room temperature and 1500 ℃
Can know that by table for silicon carbide ceramics matrix material, sticker has adhesive property preferably equally, at high temperature bonding force obtains certain enhancing between sticker and silit, increases so the shearing resistance under 1500 ℃ is compared with room temperature.
Embodiment 12
The proportioning of each component of sticker that provides according to table 11; Add 1 part of Di Cumyl Peroxide 99; Mixing, the degassing (pressure is-0.05MPa that the time is 5 minutes), 160 ℃ of curing are after 2 hours, with its sticker as carbon fibre reinforced silicon carbide composite material; Process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is as shown in table 12.
The composition of table 11 sticker and proportioning
D wherein
3 NBe pregnancy basic ring three silazane.
The Si-B-C-N polymkeric substance is first part synthetic (embodiment 5 is synthetic)
The shearing resistance of table 12 sticker under room temperature and 1500 ℃
Can know that by table for the carbon fibre reinforced silicon carbide body material, sticker has adhesive property preferably equally.
Embodiment 13
The proportioning of each component of sticker that provides according to table 13; Add a two (2,4 dichloro benzene formyl) superoxide, (pressure is-0.05MPa for mixing, the degassing; Time is 5 minutes), 160 ℃ solidify after 2 hours; With its sticker as graphite substrate material, process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is as shown in table 14.
The composition of table 13 sticker and proportioning
MM wherein
NBe hexamethyldisilazane.
The Si-B-C-N polymkeric substance is first part synthetic (embodiment 6 is synthetic).
The shearing resistance of table 14 sticker under room temperature and 1500 ℃
Can know by table,, can improve the room temperature cohesive strength of sticker, keep higher adhesive property under the high temperature simultaneously through changing the composition and the proportioning of sticker.
Embodiment 14
The proportioning of each component of sticker that provides according to table 15 adds 1 part of Di Cumyl Peroxide 99, and (pressure is-0.05MPa for mixing, the degassing; Time is 5 minutes), 160 ℃ solidify after 2 hours; With its sticker as the stainless steel base material, process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is shown in table 16.
The composition of table 15 sticker and proportioning
MM wherein
NBe hexamethyldisilazane.
The Si-B-C-N polymkeric substance is first part synthetic (embodiment 1 is synthetic).
The shearing resistance of table 16 sticker under room temperature and 1000 ℃
Can know that by table this sticker has adhesive property preferably for metallic substance.Mainly be through changing the composition and the proportioning of sticker, adjust the thermal expansivity of sticker, reducing the thermal stresses between sticker and metallic substance, thereby make sticker at high temperature keep higher adhesive property.
Embodiment 15
The proportioning of each component of sticker that provides according to table 17; Add a two (2,4 dichloro benzene formyl) superoxide, (pressure is-0.05MPa for mixing, the degassing; Time is 5 minutes), 170 ℃ solidify after 2 hours; With its sticker as the stainless steel base material, process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is shown in table 18.
The composition of table 17 sticker and proportioning
MM wherein
NBe hexamethyldisilazane.
The silicon-carbon nitrogen polymer is first part synthetic (embodiment 7 is synthetic).
The shearing resistance of table 18 sticker under room temperature and 1000 ℃
Can know by table, change the composition and the proportioning of sticker, bigger to the high temperature bond performance impact between metal base.
Embodiment 16
The proportioning of each component of sticker that provides according to table 19; The Di Cumyl Peroxide 99 that adds 1 part; Mixing, the degassing (pressure is-0.05MPa that the time is 5 minutes), 160 ℃ of curing are after 2 hours, with its sticker as the titanium alloy substrate material; Process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is shown in table 20.
The composition of table 19 sticker and proportioning
D wherein
3 NBe pregnancy basic ring three silazane.
The silicon-carbon nitrogen polymer is first part synthetic (embodiment 4 is synthetic).
The shearing resistance of table 20 sticker under room temperature and 1000 ℃
Can know that by table for the titanium alloy substrate material, this sticker has room temperature and high temperature bond performance preferably equally.
Embodiment 17
The proportioning of each component of sticker that provides according to table 21; Add a two (2,4 dichloro benzene formyl) superoxide, (pressure is-0.05MPa for mixing, the degassing; Time is 5 minutes), 170 ℃ solidify after 2 hours; With its sticker as steel as matrix material, process 5 groups of bonding piece, measure its room temperature and high-temperature behavior.The result is shown in table 22.
The composition of table 21 sticker and proportioning
D wherein
3 NBe pregnancy basic ring three silazane.
The silicon-carbon nitrogen polymer is first part synthetic (embodiment 4 is synthetic).
The shearing resistance of table 22 sticker under room temperature and 1000 ℃
No matter can be known by table, for the composition and the proportioning that change sticker, be metal, pottery or composite material base, and the influence of room temperature adhesive property is less, mainly is the high-temperature behavior that influences sticker.
Claims (10)
1. method for preparing the Si-B-C-N polymkeric substance; Comprise the steps: in inert atmosphere, chloroborane, ammonia source compound, solvent and at least two kinds of chlorosilanes are mixed react, after reaction system is alkalescence, stop to feed said ammonia source compound; Be warming up to room temperature; Under inert atmosphere protection,, vacuumize behind the merging filtrate to remove and desolvate, obtain said Si-B-C-N polymkeric substance with said solvent filter reaction system.
2. method according to claim 1 is characterized in that: in the said chlorosilane, have at least a kind of for containing the chlorosilane of silicon-alkene structures; In the said chlorosilane that contains silicon-alkene structures, said silicon-alkene structures is that the total number of carbon atoms is the alkenyl of 2-4; Said containing in the alkenyl that substituent the total number of carbon atoms is 2-4, said substituting group is selected from least a in methyl, ethyl and the chlorine;
The preferred RSiCl of said chlorosilane
3, R
2SiCl
2And R
3Among the SiCl at least two kinds; Wherein, said R be hydrogen, the total number of carbon atoms be 1-6 alkyl, naphthenic base that the total number of carbon atoms is 3-6, contain naphthenic base that substituent the total number of carbon atoms is 3-6, alkenyl that the total number of carbon atoms is 2-4, aryl that the total number of carbon atoms is 6-10, contain substituent the total number of carbon atoms and be the alkenyl of 2-4 and contain at least a in the aryl that substituent the total number of carbon atoms is 6-10; Said contain naphthenic base that substituent the total number of carbon atoms is 3-6, contain substituent the total number of carbon atoms be the alkenyl of 2-4 and contain in the aryl that substituent the total number of carbon atoms is 6-10 that said substituting group is selected from least a in methyl, ethyl and the chlorine;
Said chlorosilane specifically is selected from the methyl ethylene dichlorosilane; The methylpropenyl dichlorosilane; Vinyl toluene base dichlorosilane; The ethyl vinyl dichlorosilane; The divinyl dichlorosilane; To the styryl dichlorosilane; Vinyl trichloro silane; The styryl trichlorosilane; The dimethyl-vinyl chlorosilane; The methylethyl vinyl chlorosilane; The phenyl vinyl dichlorosilane; The methyl phenyl vinyl chlorosilane; Dichlorosilane; Dimethyl dichlorosilane (DMCS); Dimethyldichlorosilane(DMCS); Diethyl dichlorosilane; Ethyl dichlorosilane; The n-propyl dichlorosilane; The dipropyl dichlorosilane; Trichlorosilane; METHYL TRICHLORO SILANE; Ethyl trichlorosilane; Phenyl-trichloro-silicane; The normal-butyl dichlorosilane; The isobutyl-dichlorosilane; The isopentyl dichlorosilane; The benzyl dichlorosilane; The naphthyl dichlorosilane; The propenyl dichlorosilane; Diphenyl dichlorosilane; Diphenyl dichlorosilane; The methylethyl dichlorosilane; The methyl ethylene dichlorosilane; Dichloromethyl phenylsilane; The dibenzyl dichlorosilane; The rubigan dichlorosilane; The n-hexyl dichlorosilane; The cyclohexyl dichlorosilane; The dicyclohexyl chlorosilane; The diisobutyl dichlorosilane; The p-methylphenyl dichlorosilane; Two pairs of phenyl chlorosilanes; To at least two kinds in styryl dichlorosilane and the ethynyl dichlorosilane;
Said chloroborane is selected from R
2BCl, RBCl
2, BCl
3, R
2NBCl
2, RN
2BCl, R
2B
3N
3Cl, RB
3N
3Cl
2And B
3N
3Cl
3In at least a; Wherein, R be hydrogen, the total number of carbon atoms be 1-6 alkyl, naphthenic base that the total number of carbon atoms is 3-6, contain naphthenic base that substituent the total number of carbon atoms is 3-6, alkenyl that the total number of carbon atoms is 2-4, aryl that the total number of carbon atoms is 6-10, contain substituent the total number of carbon atoms and be the alkenyl of 2-4 and contain at least a in the aryl that substituent the total number of carbon atoms is 6-10; Said contain naphthenic base that substituent the total number of carbon atoms is 3-6, contain substituent the total number of carbon atoms be the alkenyl of 2-4 and contain in the aryl that substituent the total number of carbon atoms is 6-10 that said substituting group is selected from least a in methyl, ethyl and the chlorine;
Said chloroborane specifically is selected from least a in a chloroborane, two chloroboranes, three chloroboranes, methyl dichloro borine, the substituted chloroborane of amido, the substituted borazine of chlorine and the trichlorine borazine;
Said ammonia source compound is selected from least a in ammonia and the organic amine; Wherein, said organic amine is selected from least a in methylamine, ethamine, quadrol, propylamine, aniline and the Ursol D;
Said solvent is selected from least a in alkane that the total number of carbon atoms is 6-10, aromatic hydrocarbons that the total number of carbon atoms is 6-8, ether that the total number of carbon atoms is 4-8 and the furans, specifically is selected from least a in hexane, toluene, YLENE, ether, the THF;
The molar ratio of said chlorosilane and said chloroborane is 1-20: 1-20, preferred 1-5: 1-5; The consumption of said solvent is said chloroborane and chlorosilane gross weight 1～10 times, preferred 2～4 times;
In the said reactions step, temperature is-20～-10 ℃, preferred-15～-12 ℃.
3. the Si-B-C-N polymkeric substance for preparing of the arbitrary said method of claim 1-2.
4. polymkeric substance according to claim 3 is characterized in that: the number-average molecular weight of said Si-B-C-N polymkeric substance is 500-3000, preferred 600-1500; 25 ℃ viscosity is 800-80000cp, preferred 900-5000cp.
5. organosilicon sticker comprises each component of following weight part:
6. organosilicon caking agent according to claim 5 is characterized in that: said organosilicon caking agent also comprises at least a in following each component: Si
3N
4, B
4C, MgO, ZrO
2, ZrC, TiN, AlN, Si, B, TiB
2, BN, Al
2O
3And superoxide;
The weight part of above-mentioned each component is respectively:
Said Si
3N
4, B
4C, MgO, ZrO
2, ZrC, TiN, AlN, Si, B, TiB
2, BN and Al
2O
3Weight part all be not 0;
Said superoxide is selected from least a in Di Cumyl Peroxide 99 and two (2,4 dichloro benzene formyl) superoxide.
7. a method for preparing claim 5 or 6 said organosilicon stickers comprises the steps: obtaining said organosilicon caking agent after claim 7 or 8 said each component mixing, the degassing and the curing.
8. method according to claim 7 is characterized in that: in the said degassing step, pressure is-0.05～-0.1MPa, the time is 5-10 minute;
In the said curing schedule, temperature is 150～200 ℃, preferred 160～180 ℃, and 1～3 hour time, preferred 2 hours.
9. the caking agent that contains claim 5 or 6 said organosilicon caking agents.
10. claim 3 or 4 said polymkeric substance or claim 5 or the 6 said organosilicon caking agents application in the preparation caking agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210068871 CN102604108B (en) | 2012-03-15 | 2012-03-15 | Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210068871 CN102604108B (en) | 2012-03-15 | 2012-03-15 | Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102604108A true CN102604108A (en) | 2012-07-25 |
| CN102604108B CN102604108B (en) | 2013-11-06 |
Family
ID=46521918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210068871 Active CN102604108B (en) | 2012-03-15 | 2012-03-15 | Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102604108B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755348A (en) * | 2013-11-22 | 2014-04-30 | 天津大学 | Silicon boron carbon nitrogen ceramic and preparation method thereof |
| CN104031603A (en) * | 2014-05-26 | 2014-09-10 | 中科院广州化学有限公司 | High-heat-conductivity boroheteropolysiloxane potting adhesive and preparation method thereof |
| CN105694049A (en) * | 2016-01-22 | 2016-06-22 | 中国人民解放军国防科学技术大学 | Preparation method of polyborosilazane |
| CN106057334A (en) * | 2016-08-02 | 2016-10-26 | 上海新益电力线路器材有限公司 | Explosion-proof sheath for wire and cable and manufacturing method thereof |
| CN107739207A (en) * | 2017-09-19 | 2018-02-27 | 东华大学 | A kind of preparation method of amorphous Si-B-C-N zirconium aluminium ceramic material |
| CN108707234A (en) * | 2018-04-26 | 2018-10-26 | 华东理工大学 | A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications |
| CN109384466A (en) * | 2017-08-10 | 2019-02-26 | 中国科学院上海硅酸盐研究所 | A kind of method that the modified PVDF hollow fiber membrane of radical initiator efficiently prepares fine and close SiBCN ceramics |
| CN111662541A (en) * | 2020-05-07 | 2020-09-15 | 北京宇航系统工程研究所 | Silicon-boron-nitrogen-alkane modified high-temperature-resistant polyurethane rubber and preparation method thereof |
| CN112867767A (en) * | 2018-09-28 | 2021-05-28 | Posco公司 | Composite resin composition for fuel tank steel plate, composite resin-coated steel plate using same, and method for producing same |
| CN113174206A (en) * | 2021-06-04 | 2021-07-27 | 成都工业学院 | High-temperature-resistant high-strength ceramic high-temperature glue, and preparation method and application thereof |
| CN114656922A (en) * | 2022-03-28 | 2022-06-24 | 北京理工大学 | Preparation method of SiBCN ceramic-based continuous adhesive film |
| CN114835904A (en) * | 2022-04-07 | 2022-08-02 | 福建立亚化学有限公司 | Preparation method of liquid polyborosilazane |
| CN115613013A (en) * | 2022-10-31 | 2023-01-17 | 中国科学院化学研究所 | Composite insulating layer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19817680A1 (en) * | 1998-04-21 | 1999-10-28 | Bayer Ag | Silicon boronitride ceramic powder is produced |
| CN101182213A (en) * | 2007-11-16 | 2008-05-21 | 东华大学 | Method for preparing silicon-boron-nitrogen ceramic fiber precursor |
| CN101700978A (en) * | 2009-11-11 | 2010-05-05 | 哈尔滨工业大学 | Method for preparing SiBCN(O) ceramic material |
-
2012
- 2012-03-15 CN CN 201210068871 patent/CN102604108B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19817680A1 (en) * | 1998-04-21 | 1999-10-28 | Bayer Ag | Silicon boronitride ceramic powder is produced |
| CN101182213A (en) * | 2007-11-16 | 2008-05-21 | 东华大学 | Method for preparing silicon-boron-nitrogen ceramic fiber precursor |
| CN101700978A (en) * | 2009-11-11 | 2010-05-05 | 哈尔滨工业大学 | Method for preparing SiBCN(O) ceramic material |
Non-Patent Citations (1)
| Title |
|---|
| RBGIS REAU ET AL.: "Formation of Nitrilimines and Diazo Compounds from Lithiated and Stannyl Diazo Derivatives: Scope and Mechanism", 《J. AM. CHEM. SOC.》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755348B (en) * | 2013-11-22 | 2015-08-19 | 天津大学 | Si-B-C-N ceramic and preparation method thereof |
| CN103755348A (en) * | 2013-11-22 | 2014-04-30 | 天津大学 | Silicon boron carbon nitrogen ceramic and preparation method thereof |
| CN104031603A (en) * | 2014-05-26 | 2014-09-10 | 中科院广州化学有限公司 | High-heat-conductivity boroheteropolysiloxane potting adhesive and preparation method thereof |
| CN105694049A (en) * | 2016-01-22 | 2016-06-22 | 中国人民解放军国防科学技术大学 | Preparation method of polyborosilazane |
| CN106057334A (en) * | 2016-08-02 | 2016-10-26 | 上海新益电力线路器材有限公司 | Explosion-proof sheath for wire and cable and manufacturing method thereof |
| CN109384466B (en) * | 2017-08-10 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | Method for efficiently preparing compact SiBCN ceramic by modifying polyborosilazane with free radical initiator |
| CN109384466A (en) * | 2017-08-10 | 2019-02-26 | 中国科学院上海硅酸盐研究所 | A kind of method that the modified PVDF hollow fiber membrane of radical initiator efficiently prepares fine and close SiBCN ceramics |
| CN107739207A (en) * | 2017-09-19 | 2018-02-27 | 东华大学 | A kind of preparation method of amorphous Si-B-C-N zirconium aluminium ceramic material |
| CN108707234A (en) * | 2018-04-26 | 2018-10-26 | 华东理工大学 | A kind of silicon boron azane ceramic forerunner polymer containing borazine, preparation method and applications |
| CN112867767A (en) * | 2018-09-28 | 2021-05-28 | Posco公司 | Composite resin composition for fuel tank steel plate, composite resin-coated steel plate using same, and method for producing same |
| CN111662541A (en) * | 2020-05-07 | 2020-09-15 | 北京宇航系统工程研究所 | Silicon-boron-nitrogen-alkane modified high-temperature-resistant polyurethane rubber and preparation method thereof |
| CN111662541B (en) * | 2020-05-07 | 2022-05-24 | 北京宇航系统工程研究所 | Silicon-boron-nitrogen-alkane modified high-temperature-resistant polyurethane rubber and preparation method thereof |
| CN113174206A (en) * | 2021-06-04 | 2021-07-27 | 成都工业学院 | High-temperature-resistant high-strength ceramic high-temperature glue, and preparation method and application thereof |
| CN114656922A (en) * | 2022-03-28 | 2022-06-24 | 北京理工大学 | Preparation method of SiBCN ceramic-based continuous adhesive film |
| CN114835904A (en) * | 2022-04-07 | 2022-08-02 | 福建立亚化学有限公司 | Preparation method of liquid polyborosilazane |
| CN115613013A (en) * | 2022-10-31 | 2023-01-17 | 中国科学院化学研究所 | Composite insulating layer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102604108B (en) | 2013-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102604108B (en) | Organic silicon binding agent and special silicon-boron-carbon-nitrogen polymer thereof | |
| CN101376711B (en) | High temperature resistant organosilicon adhesive, special silicon nitrogen polymer therefore and preparation | |
| CN102167832B (en) | Poly(carborane-siloxane/silazane) polymer and preparation method thereof | |
| CN102675649B (en) | Polycarbosilane and preparation method thereof | |
| CN102618955B (en) | Preparation method and application of ultrahigh molecular weight polyethylene/graphene composite fiber | |
| US9045374B2 (en) | Formation of silicon carbide-silicon nitride nanoparticle carbon compositions | |
| CN101240070B (en) | Method for synthesizing supercritical fluid of ceramic precursor polycarbosilane | |
| WO2010097051A1 (en) | Room-temperature curable epoxy structural adhesive composition and preparation method thereof | |
| CN102942896B (en) | Single-component addition type high adhesion organic silicon rubber | |
| CN106046386A (en) | Epoxy resin-organosilicon polymer and preparation method and application thereof | |
| CN103553637B (en) | Cubic boron nitride glomerocryst composite with surface coating structure and preparation method thereof | |
| CN102660030B (en) | Preparation method of Si-C-N ceramic precursor | |
| CN101274941A (en) | Preparation for polyborosilazanes precursor | |
| CN103965820B (en) | High strength underwater structure glue and preparation method thereof | |
| CN108148532B (en) | A kind of normal temperature cure organic-inorganic composite high-temperature Resistance Adhesives and preparation method thereof | |
| CN104194717A (en) | Preparation method for high-temperature-resistant ceramic precursor adhesive | |
| CN103772709A (en) | Si/C/Zr ceramic precursor and preparation method thereof | |
| CN102504258A (en) | Method for preparing high-temperature resisting organic adhesive by utilizing liquid silicon carbide precursor | |
| CN105112010A (en) | Room-temperature curing adhesive based on silazane and modified silazane polymer and preparation method thereof | |
| CN104744706B (en) | The synthetic method of high ceramic yield Polycarbosilane | |
| CN108166101B (en) | High-temperature-resistant lithium-containing silicon carbide fiber and preparation method thereof | |
| CN105384940A (en) | Synthetic method of spinning grade polyaluminocarbosilane precursor | |
| CN101857789A (en) | Epoxy silsesquioxane/epoxy resin hybridized glue for packaging photoelectric devices and preparation method thereof | |
| CN109369918A (en) | A kind of high boron content Si-B-C-N presoma and preparation method thereof | |
| CN108485276B (en) | Polycarbosilane and polysiloxane resin based ablation-resistant composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |