CN113461947A - Linear polysiloxane and ceramifiable polysiloxane composition and preparation method thereof - Google Patents
Linear polysiloxane and ceramifiable polysiloxane composition and preparation method thereof Download PDFInfo
- Publication number
- CN113461947A CN113461947A CN202010241335.8A CN202010241335A CN113461947A CN 113461947 A CN113461947 A CN 113461947A CN 202010241335 A CN202010241335 A CN 202010241335A CN 113461947 A CN113461947 A CN 113461947A
- Authority
- CN
- China
- Prior art keywords
- gas
- silicone oil
- polysiloxane
- parts
- alcohol
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
Abstract
The invention relates to a linear polysiloxane, a ceramifiable polysiloxane composition and preparation thereof. The invention takes hydrogen-containing silicone oil and alcohol compounds as raw materials, and adopts a solvent-free system for preparation, so that linear polysiloxane with alkoxy on the side group can be obtained. In addition, the preparation process provided by the invention is safer and more environment-friendly, and does not need complex processes and equipment.
Description
Technical Field
The invention relates to the technical field of polysiloxane, in particular to linear polysiloxane, a ceramifiable polysiloxane composition taking the linear polysiloxane as a matrix and a preparation method thereof.
Background
With the development of industries such as aviation, aerospace, electronics and the like towards high speed and high integration, people have higher and higher requirements on high temperature resistant materials, and besides the requirements on high temperature resistance, chemical corrosion resistance and the like, the materials and the preparation process are also required to be environment-friendly, the curing process is simple, the materials can be cured on site, and the materials have flame retardance and the like.
Among high temperature resistant materials, the ceramic material with polymer as the matrix has the characteristic of 'high temperature calcination or rapid sintering into ceramic shape by combustion', can protect the internal material from being directly burned by flame, and has been widely applied in the fields of cable industry, aviation, aerospace and the like. Among them, there is a kind of ceramic material whose substrate is polysiloxane, and its main chain is siloxane bond, and its bond energy is high, so that its substrate self-body has good heat resistance. At present, polysiloxane used as a polymer-based ceramifiable material is mainly silicon rubber and silicon resin, and the ceramifiable silicon rubber has better flexibility than the ceramifiable silicon resin, so the ceramifiable silicon rubber is widely used in the cable industry.
Chinese patent CN105694471A proposes a preparation method of ceramic fire-resistant silicone rubber, which comprises the following components: methyl vinyl silicone rubber is used as a substrate, a porcelain forming filler, a fluxing agent, a catalyst, a cross-linking agent and an auxiliary agent are added, a flame retardant is additionally added, a high-temperature low-pressure preparation method is adopted in the preparation process, the ceramizable fire-resistant silicone rubber is finally obtained, and the mass fraction of the ceramizable product obtained after calcination at 1000 ℃ is not more than 80%. The method has the problems that the ceramic silicon rubber can achieve the flame retardant effect only by adding a flame retardant additionally, and the ceramic silicon rubber is molded by adopting high temperature and low pressure in the preparation process, so that the preparation process is complex.
In addition to silicone rubber as a substrate, silicone resin can also be used as a substrate, and has more advantages in flame retardancy, and flame retardant effect can be achieved without adding a flame retardant additionally.
Chinese patent CN105778504A proposes a preparation method of a ceramized silicone resin composition. The preparation method of the ceramic silicon resin composition comprises the steps of (1) dissolving 50-100 parts of condensed type silicon resin in an organic solvent, and after the condensed type silicon resin is completely dissolved, respectively adding 0.00001-2 parts of a catalyst, 5-80 parts of a porcelain forming filler, 0.01-50 parts of a fluxing agent, and other non-porcelain forming fillers and auxiliaries to obtain the ceramic silicon resin composition. (2) The composition is coated on glass fiber cloth, is baked for 5 minutes at 170 ℃ in an oven to obtain a prepreg, and is then placed in a vacuum hot press to be pressed for 3 hours at the pressure of 3MPa and the temperature of 220 ℃ to obtain a laminated board. The main problems of the method are as follows: the condensed silicone resin used by the ceramic silicone resin composition needs to be dissolved in an organic solvent firstly, and a large amount of organic solvent is used during curing, so that the ceramic silicone resin composition is not environment-friendly; in addition, water molecules are released in the curing process, a cured product can be prepared only under the conditions of high temperature and high pressure, the curing process is complex, and the inside of the cured product is porous, so that the performance is influenced.
Chinese patent CN101153076A proposes a method for preparing silicone resin with side group containing alkoxy. The preparation method of the side alkoxy silicon resin comprises the following steps: the preparation method comprises the steps of carrying out alcoholysis reaction on methyl hydrogen-containing silicone oil, stirring and mixing the hydrogen-containing silicone oil with the silicon-hydrogen functional group content of 0.01-1.67 mol/100g, an alcohol substance, an organic solvent and a catalyst in a reactor, and reacting at the temperature lower than the boiling point of the organic solvent. The side alkoxy silicon resin is liquid at room temperature, and has the advantages of high temperature resistance, room temperature curing and the like. However, the preparation process is carried out in an organic solvent system, an organic mixture is generated in the post-treatment process, the organic mixture can be utilized only by further separation, the environment is not protected, and the reaction temperature of the system is limited by the boiling point of the organic solvent.
The existing ceramifiable polysiloxane mainly comprises silicon rubber and silicon resin, but the existing ceramifiable polysiloxane is complex in curing process, curing modes such as high temperature and high pressure are mostly adopted, some ceramifiable silicon rubber can achieve a flame-retardant effect only by adding a flame retardant additionally, a solvent is required in most of the preparation processes of the silicon resin and the silicon rubber, the synthetic route is not environment-friendly, most ceramifiable polysiloxane needs to be dissolved by an organic solvent in the preparation process, a large amount of organic solvent is volatilized in the curing process, and environmental pollution is caused, so that the ceramifiable silicon resin which is environment-friendly, halogen-free, non-combustible or flame-retardant in the high polymer matrix synthetic route and simple in curing mode is needed.
Disclosure of Invention
The invention improves the prior art, adopts a solvent-free system to prepare the linear polysiloxane, is safe and environment-friendly, and can be cured at room temperature; and the linear polysiloxane is used as a matrix to prepare the ceramifiable polysiloxane composition which is non-combustible, high in heat resistance and high in mass residue rate. The ceramifiable polysiloxane composition is non-combustible in fire at normal temperature, forms a hard self-supporting ceramifiable product after continuous combustion or high-temperature calcination and cooling, has certain strength, can bear certain impact force, and can effectively isolate and protect internal materials.
One of the objects of the present invention is to provide a linear polysiloxane having the structural formula
In the formula (I), the compound is shown in the specification,
R1、R2independently selected from alkyl or aralkyl with 1-8 carbon atoms, preferably at least one selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-pentyl, isopentyl, neopentyl, octyl and benzyl;
X1、X2independently selected from one of methyl, hydroxyl, alkoxy or trimethylsiloxy;
m is not less than 1 and not more than 6000, preferably not less than 20 and not more than 6000;
n is 0. ltoreq. n.ltoreq.7000, preferably 0. ltoreq. n.ltoreq.1000;
p is 0. ltoreq. p.ltoreq.7000, preferably 0. ltoreq. p.ltoreq.100.
The second object of the present invention is to provide a method for preparing the linear polysiloxane, which comprises: mixing silicone oil and alcohol substances, and reacting to obtain the linear polysiloxane;
the silicone oil is hydrogen-containing silicone oil, and is at least one selected from methyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil, methylphenyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil, methyl methoxy silicone oil, methyl ethoxy silicone oil and methyl hydroxy silicone oil, preferably at least one selected from methyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil and methylphenyl hydrogen-containing silicone oil;
the content of the silicon-hydrogen functional groups in the silicone oil is 0.01-1.67 mol/100 g;
the alcohol substance is selected from aliphatic alcohol or aromatic alcohol with 1-8 carbon atoms, and preferably is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-octanol and benzyl alcohol;
the molar ratio of the silicon-hydrogen functional group in the silicone oil to the hydroxyl functional group in the alcohol substance is 1: (1.1-20), preferably 1: (2-20).
In the preparation process of the linear polysiloxane, the lowest reaction temperature is 0 ℃, the highest reaction temperature is the reflux temperature of the mixed solution, and the reaction time is 5-24 hours; after the reaction, unreacted alcohol was distilled off.
In the preparation process of the linear polysiloxane, a catalyst is added, the catalyst is dissolved in an alcohol substance to form a catalyst solution before being added, and the dosage ratio of the catalyst to the alcohol substance in the added catalyst solution is 1: 80-1: 100. the mass ratio of the catalyst to the hydrogen-containing silicone oil is (0.01-5): 100, preferably (0.01 to 1): 100, respectively; wherein, the catalyst is selected from at least one of alkali metal hydroxide, tetramethyl ammonium hydroxide, platinum-containing complex and copper powder, preferably at least one of tetramethyl ammonium hydroxide, chloroplatinic acid and sodium hydroxide; the alcohol substance is selected from aliphatic alcohol or aromatic alcohol with 1-8 carbon atoms, preferably at least one selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-octanol and benzyl alcohol. In the reaction process, the dropping speed of the catalyst solution is 1-20 drops/min.
After the reaction, a neutralizing agent may be added to neutralize the catalyst, and the neutralizing agent is at least one selected from the group consisting of inorganic acids, organic acids, acidic cation exchange resins, and basic anion exchange resins, preferably at least one selected from the group consisting of acidic cation exchange resins and basic anion exchange resins.
The present invention also provides a ceramifiable polysiloxane composition comprising the linear polysiloxane or the linear polysiloxane obtained by the above-mentioned production method.
The ceramifiable polysiloxane composition further comprises a curing catalyst, wherein the curing catalyst is selected from at least one of organic tin compounds, amines, acid anhydrides, titanic acid esters or platinum-containing complexes, and is preferably selected from at least one of stannous octoate, dibutyltin dilaurate, polyether amine, butyl titanate and platinum-containing complexes;
the ceramic material also contains a ceramic forming filler, wherein the ceramic forming filler is selected from silicates, preferably phyllosilicates which have a crystal structure and have the characteristics of high melting point and high sintering degree, and the ceramic forming filler is more preferably selected from at least one of mica powder, wollastonite, talcum powder and kaolin;
the ceramic filler also contains a fluxing agent, wherein the fluxing agent is a substance which can be melted at a lower temperature, plays a role of liquid phase bridging ceramic filler in a system and can be solidified after being cooled, and is selected from at least one of boron oxide, zinc borate and glass powder;
the ceramic polysiloxane also contains a thixotropic agent, wherein the thixotropic agent is a substance which is added in the preparation process of the ceramic polysiloxane and can increase the viscosity of a system so as to effectively improve the deposition of the filler; the thixotropic agent is selected from inorganic compounds, preferably at least one selected from silica, bentonite and calcium carbonate, more preferably at least one selected from fumed silica, precipitated silica, organic bentonite and nano calcium carbonate;
the ceramic material also contains active filler, wherein the active filler is a substance which can react with the ambient atmosphere or pyrolysis products in the process of heating or flame burning of the ceramizable silicon resin to ensure that the system quality is stable, so that the ceramization yield is improved, the ceramic body is more compact and compact, and various performances of the ceramic body are improved, and the active filler is selected from at least one of boron carbide, magnesium powder and aluminum powder.
The ceramifiable polysiloxane composition comprises 100 parts by mass of linear polysiloxane; 0.01-5 parts of curing catalyst, preferably 0.01-2 parts; 5-80 parts of porcelain forming filler, preferably 10-80 parts; 0.1-40 parts of fluxing agent, preferably 5-40 parts; 0.1-20 parts of thixotropic agent, preferably 1-20 parts; 0.1-20 parts of active filler, preferably 0.1-15 parts.
The ceramifiable polysiloxane composition can also be added with other common auxiliary agents, such as a curing accelerator, a silane coupling agent, a dispersing agent, a coloring agent and the like, and the auxiliary agents can be added singly or in a mixture of two or more.
The fourth purpose of the invention is to provide a preparation method of the ceramifiable polysiloxane composition, which comprises the steps of fully mixing the components including the linear polysiloxane and the curing catalyst; preferably, the preparation method comprises the steps of mixing the linear polysiloxane and a curing catalyst, then sequentially adding a porcelain forming filler, a fluxing agent, a thixotropic agent and an active filler, and fully mixing to obtain the ceramifiable polysiloxane composition. The ceramic polysiloxane composition obtained after mixing is further subjected to curing treatment, wherein the curing condition is 10-100 ℃, the relative humidity is 20-100%, and the curing time is 8-72 h.
The invention improves the prior art, provides a solvent-free system for preparing polysiloxane with side groups containing alkoxy groups, and the obtained linear polysiloxane is liquid at room temperature. The preparation of side alkoxy polysiloxane by a solvent-free system mainly has the problem of heterogeneous reaction, alcohol substances are incompatible with hydrogen-containing silicone oil, if the alcohol substances and the hydrogen-containing silicone oil are not fully stirred, the system can be subjected to phase separation, the catalyst can only exist in one phase when being added, if the catalyst exists in the alcohol substances, the reaction does not occur, and if the catalyst exists in the hydrogen-containing silicone oil, the gel phenomenon can be caused. Therefore, when the side alkoxy polysiloxane is prepared by the solvent-free method, the side alkoxy polysiloxane is fully stirred before the catalyst is added, and the catalyst is slowly added dropwise. When the reaction has proceeded to a certain extent, part of the hydrosilicon functions are substituted by alkoxy groups, and the polysiloxane with alkoxy groups in its side groups acts as a compatibilizer, so that the system becomes homogeneous. Because the alcoholysis reaction releases a large amount of hydrogen and heat, the heterogeneous system enables the reaction to be slow in the early stage, and the safe reaction is facilitated. When the system is homogeneous, the reaction rate is accelerated, so that the reaction can be completed in a shorter time. The alcohol substance obtained in the post-treatment process can be directly used for feeding in the next reaction without being separated from the organic solvent, so that the cost is saved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the linear polysiloxane provided by the invention is prepared by a solvent-free system, is safer and more environment-friendly, is in a linear structure, and is in a liquid state at normal temperature; the alcohol substance obtained in the post-treatment process can be directly used for feeding in the next reaction without being separated from the organic solvent, so that the cost is saved;
(2) the linear polysiloxane can be cured in the air at normal temperature and normal pressure, only the humidity needs to be adjusted, complex processes and equipment are not needed, and the curing process is simple;
(3) the linear polysiloxane system has high mass fraction of residues after high-temperature calcination, is slowly heated in the air atmosphere, the quality of the system is firstly reduced and then increased, and the ceramic body structure is more compact;
(4) the linear polysiloxane has the advantages of no halogen, environmental protection, non-inflammability and the like, and has wide application prospect in the fields of aviation, aerospace, electronics and the like.
Drawings
FIG. 1 is an infrared spectrum of a pendant methoxypolysiloxane obtained in example 1;
FIG. 2 is an infrared spectrum of methyl hydrogen silicone oil;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the side methoxypolysiloxane obtained in example 1;
FIG. 4 is a nuclear magnetic hydrogen spectrum of methyl hydrogen-containing silicone oil;
FIG. 5 is an IR spectrum of a pendant methoxyphenylpolysiloxane obtained in example 3;
FIG. 6 is an IR spectrum of a side-n-butoxy polysiloxane obtained in example 4;
FIG. 7 is a graph of the thermogravimetric plot of the ceramifiable polysiloxane composition obtained in example 5;
FIGS. 8a to c are schematic diagrams of ceramifiable silicone resins obtained in example 5, comparative example 1 and comparative example 2 in this order.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test instruments and test conditions used in the examples were as follows:
TABLE 1 test Instrument conditions used in the examples
| Device name | Model number | Manufacturer of the product | Test conditions/standards |
| Fourier transform infrared spectrometer | Alpha-T | Bruker, Germany | Wave number: 4000-500 cm-1 |
| Nuclear magnetic resonance apparatus | AV400 | Bruker Nano, Inc. | 400MHz |
| Thermal analyzer | Q50 | TA Corp of USA | The heating rate is 10 ℃/min |
| Oxygen index tester | JF-3 | Analytical instrument for Jiangning in Nanjing | GB/T2406-1993 |
| Vertical combustion instrument | CFZ-6 | Analytical instrument for Jiangning in Nanjing | GB/T2408-1996 |
| Electronic universal material | CMT4204 | Metas industrial system | GB/T1448-2005 |
Sources of compounds used in the examples:
TABLE 2 raw materials and sources used in the examples
| Name of medicine | Specification of | Manufacturer of the product |
| Methyl hydrogen-containing silicone oil | Industrial grade | SHANDONG DONGYUE ORGANIC SILICON MATERIAL Co.,Ltd. |
| Tetramethyl ammonium hydroxide | Analytical purity | Shanghai Mecline BioAgents Ltd |
| Methanol | Analytical purity | BEIJING CHEMICAL PLANT |
| Ethanol | Analytical purity | BEIJING CHEMICAL PLANT |
| N-butanol | Analytical purity | BEIJING CHEMICAL PLANT |
| Chloroplatinic acid | Analytical purity | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Fumed silica | Chemical purity | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Mica powder | Chemical purity | Shenzhen Haiyang Powder Technology Co., Ltd. |
| Boron carbide | Analytical purity | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Zinc borate | Analytical purity | BEIJING CHEMICAL PLANT |
| Wollastonite | Chemical purity | Shenzhen Haiyang Powder Technology Co., Ltd. |
| Glass powder | Chemical purity | Shenzhen Haiyang Powder Technology Co., Ltd. |
| Butyl titanate | Analytical purity | Tianjin chemical reagent factory |
| Dibutyl tin dilaurate | Analytical purity | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
| Polyether amine (D230) | Industrial grade | Shanghai Sen chemical technology Co Ltd |
| Acidic cation exchange resin | Chemical purity | Shanghai Mecline BioAgents Ltd |
| Basic anion exchange resin | Chemical purity | Shanghai Mecline BioAgents Ltd |
Preparation of Linear polysiloxanes
Example 1
Polysiloxane (PMOS) with side group containing methoxyl, and the raw materials and the using amounts are as follows: 100 parts of methyl hydrogen-containing silicone oil with the silicon-hydrogen functional group content of 1.6mol/100g, 1024 parts of methanol, wherein the molar ratio of the silicon-hydrogen functional group to the methanol functional group is 1: 20, 0.1 portion of tetramethylammonium hydroxide and 0.1 portion of acidic cation exchange resin.
The preparation method of the side methoxy polysiloxane comprises the following steps:
(1) weighing methyl hydrogen-containing silicone oil and methanol according to the proportion, placing the methyl hydrogen-containing silicone oil and the methanol in a three-neck flask, and stirring;
(2) after methyl hydrogen-containing silicone oil and methanol are fully mixed, slowly dripping 1 wt% of tetramethyl ammonium hydroxide methanol solution at the dripping speed of 20 drops/min and the reaction temperature of 10 ℃ for 5 hours;
(3) when no bubble is generated in the system, and an infrared spectrogram is combined to confirm that the characteristic peak of the silicon-hydrogen functional group of the hydrogen-containing silicone oil disappears, adding 1 part of acidic cation exchange resin as a neutralization catalyst into the system, stirring for 0.5h, and filtering to obtain clear liquid; and separating the residual methanol from the system by adopting a reduced pressure distillation method, storing for later use, and obtaining the rest products, wherein the temperature is 30 ℃ and the vacuum degree is about 0.7MPa during the reduced pressure distillation.
The synthesized product is liquid at room temperature, and is subjected to infrared characterization (shown in figure 1) and comparison with an infrared spectrogram (shown in figure 2) of methyl hydrogen-containing silicone oil, wherein the infrared spectrogram is 2671cm-1The characteristic peak of the silicon hydrogen at the position disappears, 2841cm-1And an obvious methoxyl vibration peak appears, and meanwhile, from the nuclear magnetic hydrogen spectrum, the chemical shift of the hydrogen-containing silicone oil (figure 4) is a characteristic peak of a hydrosilyl group at 4.7, the characteristic peak at 4.7 of the synthesized product PMOS (figure 3) disappears, and the characteristic peak of methoxyl appears at 3.55. It can thus be seen that the successful introduction of methoxy groups into the polysiloxane side chains using a solvent-free system yields a pendant methoxy Polysiloxane (PMOS) of the formula:
wherein m is 500 and n is 0.
Example 2
Polysiloxane (PMOS) with side group containing methoxyl, and the raw materials and the using amounts are as follows: 100 parts of methyl hydrogen-containing silicone oil with the silicon-hydrogen functional group content of 1.6mol/100g, 102.4 parts of methanol, and the molar ratio of the silicon-hydrogen functional group to the methanol functional group is 1: 0.1 part of tetramethylammonium hydroxide and 0.1 part of acidic cation exchange resin, wherein the methanol used is separated from the solution obtained in example 1. The preparation method of the side methoxy polysiloxane is the same as that of example 1, and the obtained product is characterized by the same structure as that of the product obtained in example 1.
Example 3
Polysiloxane (PMOSS) with side groups containing methoxy and phenyl, which is prepared from the following raw materials in percentage by weight: 100 parts of methyl hydrogen-containing silicone oil with the silicon-hydrogen functional group content of 0.75mol/100g, 50 parts of phenyl hydrogen-containing silicone oil with the silicon-hydrogen functional group content of 0.1mol/100g, 68 parts of methanol, and the molar ratio of the silicon-hydrogen functional group to the methanol functional group is 1: 5, chloroplatinic acid catalyst 0.01 part, and basic anion exchange resin 0.01 part.
The preparation method of the side methoxy polysiloxane comprises the following steps:
(1) weighing methyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil and methanol according to the proportion, putting the mixture into a three-neck flask, and stirring;
(2) after hydrogen-containing silicone oil and ethanol are fully mixed, slowly dripping 1 wt% chloroplatinic acid-isopropanol solution at the dripping speed of 10 drops/min and the reaction temperature of 30 ℃ for reaction for 20 hours;
(3) when no bubble is generated in the system and the disappearance of the characteristic peak of the silicon-hydrogen functional group of the hydrogen-containing silicone oil is confirmed by combining an infrared spectrogram, 0.01 part of basic anion exchange resin is put into the system to neutralize the chloroplatinic acid catalyst, and the clear liquid is obtained after stirring for 0.5h and filtering. And separating the residual methanol from the system by adopting a reduced pressure distillation method, storing for later use, and obtaining the rest products, wherein the temperature is 30 ℃ and the vacuum degree is about 0.7MPa during the reduced pressure distillation.
The synthesis product was liquid at room temperature and characterized by an infrared spectrum (FIG. 5), which was 2841cm-1The peak of methoxyl vibration appears at 1492, 1453 and 1406cm-1The characteristic peak of the benzene ring appears, so that the synthesized product can be determined to contain both methoxy and benzene rings, namely side methoxy phenyl Polysiloxane (PMOSS), and the structural formula is as follows:
wherein m is 30, n is 1000, and p is 30.
Example 4
Polysiloxane (PBOS) containing n-butoxy groups on side groups, which is prepared from the following raw materials in an amount: 100 parts of methyl hydrogen-containing silicone oil with the silicon hydrogen functional group content of 1mol/100g, 222 parts of n-butanol, and the molar ratio of the silicon hydrogen functional group to the n-butanol functional group of 1: 3, 0.1 part of sodium hydroxide and 0.1 part of acidic cation exchange resin.
The preparation method of the side n-butoxy polysiloxane comprises the following steps:
(1) weighing methyl hydrogen-containing silicone oil and n-butanol according to the proportion, placing the methyl hydrogen-containing silicone oil and the n-butanol into a three-neck flask, and stirring;
(1) after methyl hydrogen-containing silicone oil and n-butyl alcohol are fully mixed, slowly dripping sodium hydroxide-n-butyl alcohol solution with the concentration of 1 wt%, wherein the dripping speed is 5 drops/min, the reaction temperature is 60 ℃, and reacting for 6 hours;
(3) when no bubble is generated in the system, and an infrared spectrogram is combined to confirm that the characteristic peak of the silicon-hydrogen functional group of the hydrogen-containing silicone oil disappears, 0.1 part of acidic cation exchange resin is used as a neutralization catalyst to be put into the system, and the solution is filtered after being stirred for 0.5h to obtain clear solution. And separating the rest n-butanol from the system by using a rotary evaporator, storing for later use, and obtaining the rest products, wherein the oil bath temperature of the rotary evaporator is 50 ℃.
The synthesized product is liquid at normal temperature and is colorless and transparent. The infrared spectrum is characterized (figure 6) at 2873cm-1A distinct characteristic peak of butanoyl appears, confirming that the product is a side n-butoxy Polysiloxane (PBOS). The PBOS has a structural formula as follows:
wherein m is 25 and n is 78.
The linear polysiloxane obtained in examples 1-4 can be stored stably for at least 24 months after being sealed, and the viscosity of the system has no obvious change.
Preparation of ceramifiable Silicone compositions
Example 5
A ceramifiable polysiloxane composition comprises the following components in parts by weight: pendant methoxy polysiloxane: 100 parts of mica powder: 10 parts, zinc borate: 5 parts, fumed silica: 20 parts of boron carbide: 15 parts of an organotin catalyst (dibutyltin dilaurate): and 2 parts.
The preparation method of the ceramifiable polysiloxane composition comprises the following steps:
(1) the side methoxy polysiloxane, mica powder, zinc borate, fumed silica, boron carbide and organic tin catalyst in the embodiment 1 are weighed according to the formula;
(2) mixing the weighed lateral methoxy polysiloxane and the organic tin catalyst, stirring at room temperature to fully mix the lateral methoxy polysiloxane and the organic tin catalyst uniformly, and adding the weighed fumed silica, mica powder, zinc borate and boron carbide in batches while stirring;
(3) the well mixed mixture was left to stand and cured at room temperature in air with a relative humidity of 100% for about 24 h.
The fire retardant effect of the ceramifiable polysiloxane composition is UL-94V0 grade, and the ceramifiable polysiloxane composition is non-combustible when meeting open fire. The thermal weight loss performance of the material is characterized, the mass fraction of the system residue is minimum and about 92% at 650 ℃ under the air atmosphere, and the mass fraction of the system residue is increased when the temperature is continuously increased. The ceramic material is placed in a muffle furnace and calcined for 0.5h at the temperature of 800 ℃ and 1000 ℃, and then the ceramic material has obvious ceramic forming effect, hard texture and uniform and nonporous surface. Therefore, the linear polysiloxane system provided by the invention has high residual quality, is slowly heated in an air atmosphere, is firstly reduced and then increased in quality, and has a more compact ceramic body structure. (see FIG. 8(a))
Example 6
A ceramifiable polysiloxane composition comprises the following components in parts by weight: pendant methoxy polysiloxane: 100 parts of mica powder: 45 parts of wollastonite: 20 parts of glass powder: 35 parts, fumed silica: 5 parts, boron carbide: 5 parts of titanate catalyst (butyl titanate): 0.1 part.
The preparation method of the ceramifiable polysiloxane composition comprises the following steps:
(1) the side methoxy polysiloxane, mica powder, wollastonite, glass powder, boron carbide and gas phase silica in example 1 are weighed according to the formula;
(2) mixing the weighed lateral methoxy polysiloxane with a titanate catalyst, stirring at room temperature to fully mix the lateral methoxy polysiloxane and the titanate catalyst uniformly, and adding the weighed mica powder, wollastonite, glass powder, fumed silica and boron carbide in batches while stirring;
(3) the well mixed mixture was left to stand and cured at room temperature in air at a relative humidity of 80% for about 30 h.
The fire retardant effect of the ceramifiable polysiloxane composition is UL-94V0 grade, and the ceramifiable polysiloxane composition is non-combustible when meeting open fire. The ceramic material is placed in a muffle furnace and calcined for 0.5h at the temperature of 800 ℃ and 1000 ℃, and then the ceramic material has obvious ceramic forming effect, hard texture and uniform and nonporous surface.
Comparative example 1
A ceramifiable polysiloxane composition comprises the following components in parts by weight: pendant methoxy polysiloxane: 100 parts of mica powder: 10 parts, zinc borate: 5 parts, fumed silica: 20 parts of organic tin catalyst (dibutyltin dilaurate): and 2 parts.
The preparation method of the ceramifiable polysiloxane composition comprises the following steps:
(1) the side methoxy polysiloxane, mica powder, zinc borate, fumed silica and organic tin catalyst in the embodiment 1 are weighed according to the formula;
(2) mixing the weighed lateral methoxy polysiloxane and the organic tin catalyst, stirring at room temperature to fully mix the lateral methoxy polysiloxane and the organic tin catalyst uniformly, and adding the weighed fumed silica, mica powder and zinc borate in batches while stirring;
(3) the well mixed mixture was left to stand and cured at room temperature in air with a relative humidity of 100% for about 24 h.
The flame retardant effect of the ceramifiable polysiloxane composition is UL-94V0 grade, and the ceramifiable polysiloxane composition is continuously slowly lost under the condition of slowly heating in the air atmosphere. The porcelain has obvious porcelain forming effect after being calcined in a muffle furnace for 0.5h at 800-1000 ℃, but the surface of the porcelain has wrinkles (as shown in figure 8 (b)).
Comparative example 2
A ceramifiable polysiloxane composition comprises the following components in parts by weight: pendant methoxy polysiloxane: 100 parts of mica powder: 45 parts of wollastonite: 20, glass powder: 35 parts, boron carbide: 5, butyl titanate catalyst: 0.1 part.
The preparation method of the ceramifiable polysiloxane composition comprises the following steps:
(1) the side methoxy polysiloxane, mica powder, wollastonite, glass powder and boron carbide in example 1 are weighed according to the formula;
(2) mixing the weighed lateral ethoxy polysiloxane with a catalyst, stirring at room temperature to fully mix the lateral ethoxy polysiloxane and the catalyst uniformly, and adding the weighed mica powder, wollastonite, glass powder and boron carbide in batches while stirring;
(3) the well mixed mixture was left to stand and cured at room temperature in air at a relative humidity of 80% for about 30 h.
The ceramifiable silicon resin composition is obviously layered after being cured, the upper bottom surface and the lower bottom surface are obviously different, the sample strips are greatly bent after being placed in a muffle furnace and calcined for 0.5h at 800-1000 ℃, and the upper bottom surface and the lower bottom surface are in different colors and different properties (as shown in figure 8 (c)).
Comparative example 3 ceramicized Silicone rubber
The mechanical properties of the ceramic body obtained after the ceramic silicon rubber is calcined are researched in the preparation, structure and performance research of ceramic silicon rubber of Master thesis of southern China university, and the three-point bending strength is only 21.2MPa at most, and the compressive strength is only 6MPa at most.
TABLE 3 mechanical Property test results of ceramic bodies obtained after calcination in examples 5 to 6 and comparative examples 1 to 2
| Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Three point bending strength/MPa | 53 | 57 | 40 | 38 | 21.2 |
| Compressive strength/MPa | 66 | 72 | 46 | 50 | 6 |
By comparing the ceramifiable polysiloxane composition prepared in example 5 with that prepared in comparative example 1, boron carbide is added into the composition in example 5, so that the ceramifiable polysiloxane composition has a smoother surface after being ceramified; by comparing the ceramifiable polysiloxane compositions prepared in example 6 with those prepared in comparative example 2, in example 6, fumed silica was added, and the resulting cured product was more uniform, non-delaminated, and free from warpage after high temperature calcination (see fig. 8). The compressive strength and three-point bending strength of examples 5 and 6 were greatly improved compared to comparative examples 1, 2 and 3 (see table 3).
Different proportions of stannous octoate and D230 are added into the PMOS prepared in example 1, the curing temperature is set to be 20 ℃, then the surface drying time, the surface condition of 72h and the curing depth of 7 days are observed, and the specific data are shown in Table 4.
TABLE 4 PMOS open time with catalyst addition
The results in Table 4 show that the surface drying time of PMOS is obviously shortened by 40-60% when the stannous octoate and the polyether amine are compounded.
Claims (10)
1. A linear polysiloxane with the structural formula
In the formula (I), the compound is shown in the specification,
R1、R2independently selected from alkyl or aralkyl with 1-8 carbon atoms, preferably at least one selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-pentyl, isopentyl, neopentyl, octyl and benzyl;
X1、X2independently selected from one of methyl, hydroxyl, alkoxy or trimethylsiloxy;
m is not less than 1 and not more than 6000, preferably not less than 20 and not more than 6000;
n is 0. ltoreq. n.ltoreq.7000, preferably 0. ltoreq. n.ltoreq.1000;
p is 0. ltoreq. p.ltoreq.7000, preferably 0. ltoreq. p.ltoreq.100.
2. A method for preparing the linear polysiloxane of claim 1, comprising: mixing silicone oil and alcohol substances, and reacting to obtain the linear polysiloxane.
3. The production method according to claim 2,
the silicone oil is hydrogen-containing silicone oil, and is selected from at least one of methyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil, methylphenyl hydrogen-containing silicone oil, ethyl hydrogen-containing silicone oil, methyl methoxy silicone oil, methyl ethoxy silicone oil and methyl hydroxy silicone oil, preferably at least one of methyl hydrogen-containing silicone oil, phenyl hydrogen-containing silicone oil and methylphenyl hydrogen-containing silicone oil; and/or the presence of a gas in the gas,
the content of the silicon-hydrogen functional groups in the silicone oil is 0.01-1.67 mol/100 g; and/or the presence of a gas in the gas,
the alcohol substance is selected from aliphatic alcohol or aromatic alcohol with 1-8 carbon atoms, and preferably is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-octanol and benzyl alcohol; and/or the presence of a gas in the gas,
the molar ratio of the silicon-hydrogen functional groups in the silicone oil to the hydroxyl functional groups in the alcohols is 1 (1.1-20), and preferably 1 (2-20).
4. The production method according to claim 2,
a catalyst is also added in the reaction, and the catalyst is dissolved in an alcohol substance to form a catalyst solution before being added; and/or the presence of a gas in the gas,
the lowest reaction temperature is 0 ℃ and the highest reaction temperature is the reflux temperature of the mixed solution; and/or the presence of a gas in the gas,
the reaction time is 5-24 h; and/or the presence of a gas in the gas,
after the reaction is finished, distilling out unreacted alcohol substances.
5. The production method according to claim 4,
the mass ratio of the catalyst to the hydrogen-containing silicone oil is (0.01-5): 100, preferably (0.01 to 1): 100, respectively; and/or the presence of a gas in the gas,
in the catalyst solution, the mass ratio of the catalyst to the alcohol substance is 1: 80-1: 100; and/or the presence of a gas in the gas,
the catalyst is selected from at least one of alkali metal hydroxide, tetramethyl ammonium hydroxide, platinum-containing complex and copper powder, preferably at least one of tetramethyl ammonium hydroxide, chloroplatinic acid and sodium hydroxide; and/or the presence of a gas in the gas,
the alcohol substance is selected from aliphatic alcohol or aromatic alcohol with 1-8 carbon atoms, and preferably is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-octanol and benzyl alcohol; and/or the presence of a gas in the gas,
in the reaction process, the dripping speed of the catalyst solution is 1-20 drops/min; and/or the presence of a gas in the gas,
after the reaction is finished, a neutralizing agent is also added to neutralize the catalyst, wherein the neutralizing agent is selected from at least one of inorganic acid, organic acid, acidic cation exchange resin and basic anion exchange resin, and is preferably selected from at least one of acidic cation exchange resin and basic anion exchange resin.
6. A ceramifiable polysiloxane composition comprising the linear polysiloxane according to claim 1 or the linear polysiloxane obtained by the production method according to any one of claims 2 to 5.
7. The ceramifiable silicone composition according to claim 6, wherein in the ceramifiable silicone composition,
the paint also contains a curing catalyst, wherein the curing catalyst is selected from at least one of organic tin, amine, acid anhydride, titanate or platinum-containing complex, preferably from at least one of stannous octoate, dibutyltin dilaurate, polyether amine, butyl titanate and platinum-containing complex; and/or the presence of a gas in the gas,
the ceramic material also contains a ceramic forming filler, wherein the ceramic forming filler is selected from silicates, preferably selected from layered silicates, and more preferably selected from at least one of mica powder, wollastonite, talcum powder and kaolin; and/or the presence of a gas in the gas,
the glass powder also contains a fluxing agent, wherein the fluxing agent is selected from at least one of boron oxide, zinc borate and glass powder; and/or the presence of a gas in the gas,
the composite material also contains a thixotropic agent, wherein the thixotropic agent is selected from inorganic compounds, preferably at least one of silicon dioxide, bentonite and calcium carbonate, and more preferably at least one of fumed silica, precipitated silica, organic bentonite and nano calcium carbonate; and/or the presence of a gas in the gas,
the composite material also contains active filler, wherein the active filler is selected from at least one of boron carbide, magnesium powder and aluminum powder.
8. The ceramifiable silicone composition according to claim 7, comprising the components in parts by mass
100 parts of linear polysiloxane; and/or the presence of a gas in the gas,
0.01-5 parts of curing catalyst, preferably 0.01-2 parts; and/or the presence of a gas in the gas,
5-80 parts of porcelain forming filler, preferably 10-80 parts; and/or the presence of a gas in the gas,
0.1-40 parts of fluxing agent, preferably 5-40 parts; and/or the presence of a gas in the gas,
0.1-20 parts of thixotropic agent, preferably 1-20 parts; and/or the presence of a gas in the gas,
0.1-20 parts of active filler, preferably 0.1-15 parts.
9. A method of preparing a ceramifiable polysiloxane composition as claimed in any one of claims 6 to 8, comprising mixing the components including the linear polysiloxane and the curing catalyst; preferably, the preparation method comprises the steps of mixing the linear polysiloxane and a curing catalyst, then sequentially adding a porcelain forming filler, a fluxing agent, a thixotropic agent and an active filler, and fully mixing to obtain the ceramifiable polysiloxane composition.
10. The preparation method according to claim 9, wherein the ceramifiable polysiloxane composition obtained after mixing is further subjected to curing treatment under the conditions of 10-100 ℃, a relative humidity of 20-100% and a curing time of 8-72 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010241335.8A CN113461947A (en) | 2020-03-31 | 2020-03-31 | Linear polysiloxane and ceramifiable polysiloxane composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010241335.8A CN113461947A (en) | 2020-03-31 | 2020-03-31 | Linear polysiloxane and ceramifiable polysiloxane composition and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113461947A true CN113461947A (en) | 2021-10-01 |
Family
ID=77865241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010241335.8A Pending CN113461947A (en) | 2020-03-31 | 2020-03-31 | Linear polysiloxane and ceramifiable polysiloxane composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113461947A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621590A (en) * | 2022-03-31 | 2022-06-14 | 哈尔滨工业大学 | 4D printing shape memory polymer capable of being ceramized and preparation method thereof |
| CN115386089A (en) * | 2022-08-29 | 2022-11-25 | 万华化学集团股份有限公司 | Preparation method and application of silane oligomer |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1081750A (en) * | 1990-12-14 | 1998-03-31 | Union Carbide Chem & Plast Co Inc | Self-curing polysiloxane capable of forming ceramic |
| CN101153076A (en) * | 2006-09-29 | 2008-04-02 | 北京化工大学 | Polysiloxane resin with lateral group containing alkoxyl, producing method and use of the same |
| CN101787133A (en) * | 2010-01-08 | 2010-07-28 | 北京化工大学 | Non-solvent liquid silicone resin and preparation method thereof |
| CN103254646A (en) * | 2013-04-28 | 2013-08-21 | 深圳市新亚新材料有限公司 | Preparation method for condensed-type RTV (room temperature vulcanized) silicone rubber cross-linking agent |
| CN105542169A (en) * | 2016-02-01 | 2016-05-04 | 江西省科学院应用化学研究所 | Preparation method for alkoxy functionalized polysiloxane |
| CN105778504A (en) * | 2014-12-25 | 2016-07-20 | 广东生益科技股份有限公司 | Ceramization silicon resin composition and prepreg and laminated board made of the same |
| CN106854435A (en) * | 2017-01-11 | 2017-06-16 | 襄阳玖润氟硅材料有限公司 | A kind of preparation method of new ceramics organic siliconresin |
-
2020
- 2020-03-31 CN CN202010241335.8A patent/CN113461947A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1081750A (en) * | 1990-12-14 | 1998-03-31 | Union Carbide Chem & Plast Co Inc | Self-curing polysiloxane capable of forming ceramic |
| CN101153076A (en) * | 2006-09-29 | 2008-04-02 | 北京化工大学 | Polysiloxane resin with lateral group containing alkoxyl, producing method and use of the same |
| CN101787133A (en) * | 2010-01-08 | 2010-07-28 | 北京化工大学 | Non-solvent liquid silicone resin and preparation method thereof |
| CN103254646A (en) * | 2013-04-28 | 2013-08-21 | 深圳市新亚新材料有限公司 | Preparation method for condensed-type RTV (room temperature vulcanized) silicone rubber cross-linking agent |
| CN105778504A (en) * | 2014-12-25 | 2016-07-20 | 广东生益科技股份有限公司 | Ceramization silicon resin composition and prepreg and laminated board made of the same |
| CN105542169A (en) * | 2016-02-01 | 2016-05-04 | 江西省科学院应用化学研究所 | Preparation method for alkoxy functionalized polysiloxane |
| CN106854435A (en) * | 2017-01-11 | 2017-06-16 | 襄阳玖润氟硅材料有限公司 | A kind of preparation method of new ceramics organic siliconresin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621590A (en) * | 2022-03-31 | 2022-06-14 | 哈尔滨工业大学 | 4D printing shape memory polymer capable of being ceramized and preparation method thereof |
| CN115386089A (en) * | 2022-08-29 | 2022-11-25 | 万华化学集团股份有限公司 | Preparation method and application of silane oligomer |
| CN115386089B (en) * | 2022-08-29 | 2023-07-11 | 万华化学集团股份有限公司 | Preparation method and application of silane oligomer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huo et al. | Synthesis of a DOPO-containing imidazole curing agent and its application in reactive flame retarded epoxy resin | |
| Chiang et al. | Synthesis, characterization and thermal properties of novel epoxy containing silicon and phosphorus nanocomposites by sol–gel method | |
| US5750643A (en) | Dehydrocoupling treatment and hydrosilylation of silicon-containing polymers, and compounds and articles produced thereby | |
| CN113461947A (en) | Linear polysiloxane and ceramifiable polysiloxane composition and preparation method thereof | |
| CN109135189B (en) | P/N/Si-containing multi-element polyphosphazene silazane flame retardant for epoxy resin and preparation method thereof | |
| TW200904878A (en) | Composite material of modified expansible graphite /modified thermosetting polymer | |
| CN112210191B (en) | Method for modifying epoxy resin through phosphorus/nitrogen/silicon synergistic flame retardation | |
| CN110256814B (en) | Preparation method of piperazine structure-containing DOPO derivative modified flame-retardant epoxy resin | |
| CN114621281B (en) | Dihydrocarbyl silicon acyl dimelamine compound of organic silicon nitrogen flame retardant and preparation method thereof | |
| CN111560112B (en) | Phosphorus-containing triazole organic amine salt flame-retardant curing agent and application thereof in epoxy resin | |
| CN106220854A (en) | A kind of hyperbranched POSS fire retardant and its preparation method and application | |
| CN113698610A (en) | Hyperbranched phosphorus-silicon-containing aliphatic amine flame-retardant curing agent, preparation method thereof and application thereof in fireproof coating | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN112979960B (en) | Carborane-containing polysiloxane and preparation method thereof | |
| CN109486105B (en) | Preparation method of epoxy resin/phenyl ferric phosphate nano composite material | |
| RU2615147C1 (en) | Method for organomagnesium oxanaluminoxanes production, binders and impregnating materials based thereon | |
| CN114835903B (en) | Boron-containing silsesquioxane and preparation method thereof, modified phenolic resin and preparation method and application thereof | |
| CN113292823B (en) | Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material | |
| CN107189442B (en) | Modified methyl phenyl silicone resin based on nano attapulgite and preparation method thereof | |
| DE4114217A1 (en) | ORGANIC SILAZANE POLYMERS, METHOD FOR THE PRODUCTION THEREOF AND A METHOD FOR THE PRODUCTION OF CERAMIC MATERIALS THEREOF | |
| CN101665506B (en) | Novel boron-and benzene-contained acetenyl oxosilane and preparation method thereof | |
| CN117070126B (en) | Corrosion-resistant water-based fireproof paint and preparation method thereof | |
| KR101941460B1 (en) | Organic-inorganic hybrid resin that consisting epoxysilylphopshate polymer attached melamine functional group and incombustible paint compositions using the same | |
| CN115850340B (en) | Eugenol-based silicon-containing flame retardant, and preparation method and application thereof | |
| CN115583982A (en) | Amine modified adenosine triphosphate flame retardant, preparation method thereof and application thereof in fireproof coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211001 |
|
| RJ01 | Rejection of invention patent application after publication |