CN110845850B - Ceramizable halogen-free flame-retardant silicone rubber and preparation method thereof - Google Patents
Ceramizable halogen-free flame-retardant silicone rubber and preparation method thereof Download PDFInfo
- Publication number
- CN110845850B CN110845850B CN201911083874.7A CN201911083874A CN110845850B CN 110845850 B CN110845850 B CN 110845850B CN 201911083874 A CN201911083874 A CN 201911083874A CN 110845850 B CN110845850 B CN 110845850B
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- parts
- halogen
- retardant
- free flame
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a porcelainized halogen-free flame-retardant silicone rubber and a preparation method thereof. The porcelainized halogen-free flame-retardant silicone rubber comprises the following raw materials: 100 parts of methyl vinyl silicone rubber, 30-50 parts of fumed silica, 30-50 parts of fluorophlogopite, 10-30 ppm of platinum compound, 1-3 parts of nitrogenous silane, 4-8 parts of hydroxyl silicone oil, 0.4-0.8 part of hydrogen-containing silicone oil and 1.5-2.5 parts of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide. During preparation, uniformly mixing methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and hydrogen-containing silicone oil in a kneading machine to obtain silicone rubber base rubber; and (3) uniformly mixing the basic adhesive and other components in the formula by using a double-roll open mill, and then vulcanizing. The silicon rubber has excellent flame retardant property and good mechanical property, and does not contain halogen; can be transformed into a ceramic structure with excellent mechanical properties in a high-temperature environment.
Description
Technical Field
The invention relates to the technical field of silicon rubber flame-retardant materials, in particular to porcelainized halogen-free flame-retardant silicon rubber and a preparation method thereof.
Technical Field
The ceramifiable flame-retardant silicone rubber composite material has excellent ceramifiable performance and good flame-retardant performance, and has important application in the fields of building engineering, aerospace, electronics and electricity and the like. When the ceramizable flame-retardant silicone rubber composite material is used as an insulating material for wrapping wires and cables, an inorganic ceramic structure can be formed in a fire disaster, flame spreading is effectively prevented, internal materials are protected from being damaged by high temperature, normal operation of a circuit is guaranteed, secondary damage such as electric leakage and electric shock is avoided, and safety of fire rescue is improved. The method has important significance for protecting the life and property safety of people.
The ceramizable flame-retardant silicone rubber composite material mainly comprises a silicone rubber matrix, a ceramic filler (talcum powder, muscovite, montmorillonite, calcium carbonate and the like), a low-melting-point fluxing agent (low-melting-point glass powder, zinc borate, boron oxide and the like), a flame retardant (magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate and the like) and the like. The ceramic filler and the silicon rubber degradation product are bonded together through a molten liquid phase generated by the low-melting-point fluxing agent at a high temperature, and a ceramic structure with certain strength is formed after the temperature is reduced. However, the fluxing agent usually needs a larger addition amount (>15 wt%) to achieve satisfactory vitrification performance, which deteriorates the mechanical properties and processability of the silicone rubber composite material, wherein the fluxing agent such as low-melting glass powder also deteriorates the flame retardant properties of the silicone rubber composite material, while the fluxing agent such as zinc borate has the problem of low flame retardant efficiency. Therefore, the silicone rubber composite material can obtain good flame retardant property by being compounded with a large amount of conventional flame retardants, which further reduces the mechanical property and the processability of the silicone rubber composite material. For example, in the chinese patent application CN 107760039 a, a porcelainized flame retardant and fire resistant silicone rubber is prepared by compounding a plurality of inorganic fillers such as aluminum hydroxide, low melting point glass powder and sericite, but because the addition amount of the filler is large (>50 wt%), the compatibility with a silicone rubber matrix is poor, and the mechanical properties are deteriorated. The Chinese invention patent application CN 106366669A takes magnesium hydroxide, mica powder, silicon carbide, platinum compound and potassium nitrate as fire-resistant components to prepare the fire-resistant silicone rubber, but the addition amount of the magnesium hydroxide needs to reach 120-140 parts. The Chinese patent application CN 106832960A adopts the compounding of calcium carbonate, ammonium polyphosphate, silicate filler, fluxing agent and the like to prepare the ceramic flame-retardant fire-resistant silicone rubber composite material, but the problems of large addition amount of inorganic filler, poor compatibility and deteriorated mechanical property exist. Guo et al prepared ceramifiable flame-retardant silicone rubber composites having certain ceramifiable and flame-retardant properties using calcium carbonate and sericite as the porcelain-forming filler, low-melting glass powder as the flux, and ammonium polyphosphate as the flame retardant, but the tensile strength of the silicone rubber composite was reduced from 10.3MPa to 5.3MPa, and the elongation at break was reduced from 450% to 283% (Preparation and properties of a ceramifiable flame-retardant silicone rubber composites, Journal of Thermal Analysis and calibration, 2017,130(2): 813-821).
In summary, some progress is made in the current research on ceramifiable flame-retardant silicone rubber composite materials, but the existing preparation method has the following defects: the low-melting point fluxing agent usually needs a larger addition amount (>15 wt%) to achieve satisfactory vitrification performance, which deteriorates the processability and mechanical properties of the silicone rubber, and also has the problems of deteriorating the flame retardant property or low flame retardant efficiency of the silicone rubber composite material, and the like. And the processing performance and mechanical property of the silicon rubber can be further damaged by adding a large amount of traditional flame retardant compounded with a fluxing agent. This greatly limits the range of applications for ceramifiable flame-retardant silicone rubber composites. Therefore, research and development of an efficient porcelain forming mode have great significance for preparing the silicon rubber with good mechanical property, flame retardant property and porcelain property.
Disclosure of Invention
The invention aims to provide the silicone rubber with excellent vitrification performance, flame retardant performance and good mechanical property aiming at the defects of the existing vitrification flame retardant silicone rubber.
The invention also aims to provide a preparation method of the porcelainized halogen-free flame-retardant silicone rubber.
The purpose of the invention is realized by the following technical scheme:
the porcelainized halogen-free flame-retardant silicone rubber comprises the following raw materials in parts by weight:
the nitrogenous silane is N-phenyl-3-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-piperazinylpropylmethyldimethoxysilane or gamma-ureidopropyltrimethoxysilane.
To further achieve the object of the present invention, preferably, the methyl vinyl silicone rubber is two kinds of methyl vinyl silicone rubber having vinyl contents of 0.05mol% to 0.10mol% and 2.0mol% to 4.0mol%, respectively, the former and the latter having a mass ratio of 98: 2-90: 10, the molecular weight of the two is 500000-700000 g/mol.
Preferably, the specific surface area of the fumed silica is 200-300 m2/g。
Preferably, the particle size of the fluorophlogopite is 800-3000 meshes.
Preferably, the platinum compound is one of an isopropanol solution of chloroplatinic acid, a tetrahydrofuran solution of chloroplatinic acid, a divinyltetramethyldisiloxane complex of chloroplatinic acid, or an olefin complex of chloroplatinic acid.
Preferably, the hydroxyl silicone oil has a hydroxyl content of 5wt% to 10 wt%.
Preferably, the hydrogen content of the hydrogen-containing silicone oil is 1.0wt% to 1.5 wt%.
The preparation method of the porcelainized halogen-free flame-retardant silicone rubber comprises the following steps:
(1) putting methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and hydrogen-containing silicone oil into a kneading machine together, mixing for 1-2 h, heating to 140-160 ℃, continuing mixing for 2-4 h, then vacuumizing and mixing for 0.5-1.5 h at 120-130 ℃, mixing uniformly, and cooling to room temperature to obtain base rubber;
(2) uniformly mixing the base rubber, the fluorophlogopite, the platinum compound and the 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide on a double-roll open mill; and vulcanizing at 160-170 ℃ for 15-30 min, and vulcanizing for two stages at 180-200 ℃ for 1-2 h to obtain the silicone rubber.
In the invention, the fluorophlogopite and platinum compound/nitrogen-containing silane system have good synergistic effect on improving the vitrification performance and the flame retardant performance of the silicone rubber. The laminar structure of the fluorophlogopite has good physical barrier effect and skeleton supporting effect, which is beneficial to inhibiting the mass and heat transfer process in the combustion process of the silicon rubber and forming a stable ceramic structure; under the action of a platinum compound/nitrogen-containing silane system, a silicon rubber molecular chain can realize organic-inorganic conversion in a high-temperature environment, and is jointly ceramized with fluorophlogopite and white carbon black, so that the silicon rubber is endowed with excellent flame retardant property and ceramization property, and therefore, fluxing agents such as low-melting-point glass powder and the like, and traditional flame retardants such as aluminum hydroxide, magnesium hydroxide, phosphorus series and the like do not need to be added into the raw materials.
Compared with the prior art, the invention has the following advantages:
1) the ceramifiable halogen-free flame-retardant silicone rubber composite material provided by the invention has the advantages that the traditional fluxing agent is not added, and the ceramifiable performance can be obviously improved only by adding a small amount of platinum-containing compound/nitrogen-containing silane system.
2) According to the invention, conventional halogen-free flame retardants such as aluminum hydroxide, magnesium hydroxide and phosphorus are not required to be added, the prepared porcelainized silicone rubber has excellent flame retardant property, and meanwhile, the silicone rubber still maintains good mechanical property and processability due to the small addition amount of the inorganic filler.
3) The porcelainized halogen-free flame-retardant silicone rubber provided by the invention is easy to obtain raw materials, simple in preparation process, capable of realizing industrial production and good in application prospect.
Drawings
Fig. 1 is a video screenshot of a vertical burning test of silicone rubber of comparative example 1.
Fig. 2 is a video screenshot of the vertical burning test of silicone rubber in example 1.
FIG. 3 is a digital photograph of a sample of the silicone rubber of comparative example 1 after being treated at 1000 ℃ for 1 hour.
FIG. 4 is a digital photograph of a sample of the silicone rubber of example 1 after being treated at 1000 ℃ for 1 hour.
FIG. 5 is an SEM photograph of a bent cross-section of a ceramic body obtained in comparative example after treatment at 1000 ℃ for 1 hour.
FIG. 6 is an SEM photograph of a bent cross-section of the ceramic body obtained in example 1 after treatment at 1000 ℃ for 1 hour.
Detailed Description
The present invention will be further described with reference to the following examples for better understanding of the present invention, but the embodiments of the present invention are not limited thereto.
Example 1
93 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 0.05mol% (molecular weight 620000g/mol), 7 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 3.0 mol% (molecular weight 640000g/mol), and 40 parts by mass of fumed silica (specific surface area 280 m)2(g), 6 parts by mass of a hydroxyl silicone oil (hydroxyl content: 8.5 wt.%), and 0.6 part by mass of a hydrogen-containing silicone oil (hydrogen content: 1.2 wt.%) were kneaded in a kneader for 1.5 hours. And then heating to 150 ℃, continuing to mix for 3h, then vacuumizing and mixing for 1h at 120 ℃, and cooling to room temperature to obtain the silicone rubber base rubber.
40 parts by mass of fluorophlogopite (3000 meshes), a divinyltetramethyldisiloxane complex of chloroplatinic acid (the addition amount is 15ppm in terms of the mass concentration of platinum in the methyl vinyl silicone rubber), 2 parts by mass of gamma-aminopropyltriethoxysilane, and 2 parts by mass of 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane were added to the above base rubber by a two-roll mill, and the mixture was uniformly mixed and then sheeted. Vulcanizing at 165 deg.C for 20min to obtain films of 3mm and 2mm, and vulcanizing at 180 deg.C for 2 hr. The 3mm thick film is used for testing flame retardant property and vitrifying property, and the 2mm film is used for testing mechanical property. The properties of the sample are shown in tables 1 and 2, wherein the video screenshot of the sample in the vertical burning test is shown in FIG. 2, the digital photograph of the ceramic body obtained after the sample is treated at 1000 ℃ for 1h is shown in FIG. 4, and the SEM photograph of the bent section of the ceramic body is shown in FIG. 6.
Example 2
98 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 0.10mol% (molecular weight 700000g/mol), 2 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 4.0mol% (molecular weight 500000g/mol), and 50 parts by mass of fumed silica (specific surface area 200 m)2(g), 8 parts by mass of a hydroxyl silicone oil (hydroxyl group content: 5 wt%) and 0.6 part by mass of a hydrogen-containing silicone oil (hydrogen content: 1.2 wt%) were kneaded in a kneader for 2 hours. And then heating to 160 ℃, continuing to mix for 2h, then vacuumizing and mixing for 0.5h at 130 ℃, and cooling to room temperature to obtain the silicone rubber base rubber.
30 parts by mass of fluorophlogopite (3000 meshes), a tetrahydrofuran solution of chloroplatinic acid (the addition amount is 15ppm in terms of the mass concentration of platinum in the methyl vinyl silicone rubber), 2 parts by mass of N-phenyl-3-aminopropyltrimethoxysilane and 1.5 parts by mass of 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane are added into the base rubber by a double-roll open mill, and the mixture is uniformly mixed and then is taken out. Vulcanizing at 160 deg.C for 30min to obtain films of 3mm and 2mm, and vulcanizing at 200 deg.C for 1 hr. The properties of the samples are shown in tables 1 and 2.
Example 3
90 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 0.05mol% (molecular weight 620000g/mol), 10 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 2.0mol% (molecular weight 640000g/mol), and 30 parts by mass of fumed silica (specific surface area 300 m)2(g), 4 parts by mass of a hydroxyl silicone oil (hydroxyl group content: 5 wt%) and 0.6 part by mass of a hydrogen-containing silicone oil (hydrogen content: 1.2 wt%) were kneaded in a kneader for 1 hour. And then heating to 140 ℃ and continuing to mix for 4h, then vacuumizing and mixing for 1.5h at 120 ℃, and cooling to room temperature to obtain the silicone rubber base rubber.
50 parts by mass of fluorophlogopite (1250 meshes), an isopropanol solution of chloroplatinic acid (the addition amount is 10ppm in terms of the mass concentration of platinum in the methyl vinyl silicone rubber), 1 part by mass of gamma-piperazinylpropylmethyldimethoxysilane and 2.5 parts by mass of 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane are added into the base rubber by a double-roll open mill, and the mixture is uniformly mixed and then is taken out. Vulcanizing at 170 deg.C for 15min to obtain films of 3mm and 2mm, and vulcanizing at 190 deg.C for 1.5 hr. The properties of the samples are shown in tables 1 and 2.
Example 4
This example was different from example 1 in that 0.6 part by mass of hydrogen-containing silicone oil (hydrogen content: 1.2 wt%) was changed to 0.4 part by mass of hydrogen-containing silicone oil (hydrogen content: 1.5 wt%); a divinyltetramethyldisiloxane complex of chloroplatinic acid (added in an amount of 15ppm in terms of the mass concentration of platinum in the methylvinylsiloxane rubber) was converted into an olefin complex of chloroplatinic acid (added in an amount of 15ppm in terms of the mass concentration of platinum in the methylvinylsiloxane rubber); 2 parts by mass of gamma-aminopropyltriethoxysilane was converted into 2 parts by mass of gamma-ureidopropyltrimethoxysilane. The properties of the samples are shown in tables 1 and 2.
Example 5
This example was different from example 1 in that 0.6 part by mass of hydrogen-containing silicone oil (hydrogen content: 1.2 wt%) was changed to 0.8 part by mass of hydrogen-containing silicone oil (hydrogen content: 1.0 wt%); converting 40 parts by mass of fluorophlogopite (3000 mesh) into 40 parts by mass of fluorophlogopite (800 mesh); divinyltetramethyldisiloxane complex of chloroplatinic acid (added in an amount of 15ppm in terms of the mass concentration of platinum in the methylvinylsiloxane rubber) to be converted into divinyltetramethyldisiloxane complex of chloroplatinic acid (added in an amount of 30ppm in terms of the mass concentration of platinum in the methylvinylsiloxane rubber); 2 parts by mass of gamma-aminopropyltriethoxysilane was converted to 3 parts by mass of gamma-piperazinylpropylmethyldimethoxysilane. The properties of the samples are shown in tables 1 and 2.
Comparative example 1
93 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 0.05mol% (molecular weight 620000g/mol), 7 parts by mass of a methyl vinyl silicone rubber having a vinyl content of 3.0 mol% (molecular weight 640000g/mol), and 40 parts by mass of white carbon black (specific surface area 280 m)2(g), 6 parts by mass of a hydroxyl silicone oil (8.5 wt%), and 0.6 part by mass of a hydrogen-containing silicone oil (1.2 wt% hydrogen content) were mixed in a kneader, and kneaded at normal temperature for 1.5 hours. And then heating to 150 ℃, continuing to mix for 3h, then vacuumizing and mixing for 1h at 120 ℃, and cooling to room temperature to obtain the silicone rubber base rubber.
2 parts by mass of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide are added into the basic rubber by a double-roll open mill, and the mixture is uniformly mixed and then is taken out. Vulcanizing at 165 deg.C for 20min to obtain films of 3mm and 2mm, and vulcanizing at 180 deg.C for 2 hr. The 3mm thick film is used for testing flame retardant property and vitrifying property, and the 2mm film is used for testing mechanical property. The properties of the sample are shown in tables 1 and 2, wherein the video screenshot of the sample in the vertical burning test is shown in fig. 1, the digital photograph of the ceramic body obtained after the sample is treated at 1000 ℃ for 1h is shown in fig. 3, and the SEM photograph of the bent section of the ceramic body is shown in fig. 5.
Comparative example 2
The comparative example is different from comparative example 1 in that 40 parts by mass of fluorophlogopite (3000 mesh) was further added to the base rubber in the open mill kneading stage. The properties of the samples are shown in tables 1 and 2.
Comparative example 3
The present comparative example is different from comparative example 1 in that a divinyltetramethyldisiloxane complex of chloroplatinic acid (the addition amount was 15ppm in terms of the mass concentration of platinum in the methylvinylsiloxane rubber) and 2 parts by mass of γ -aminopropyltriethoxysilane were further added to the base rubber in the kneading stage by an open mill. The properties of the samples are shown in tables 1 and 2.
Performance test method
1. The tensile strength and elongation at break of the silicone rubber were measured according to GB/T528-2009, with a tensile rate of 500 mm/min.
2. The tear strength of the silicone rubber was measured in accordance with GB/T529-2008, and the tensile rate was 500 mm/min.
3. The Shore A hardness of the silicone rubber is determined according to GB/T531-2008.
4. The Limiting Oxygen Index (LOI) of the silicone rubber was determined according to ASTM D2863-.
5. The vertical burning rating (UL-94) of the silicone rubber was determined according to ASTM 635 and 2003.
6. And (4) determining the vitrification performance of the silicone rubber according to GB/T14390-2008. At room temperature, a silicon rubber sample with the sample size of 80mm multiplied by 10mm multiplied by 3mm is put into a muffle furnace, the temperature is raised to 1000 ℃ at the heating rate of 10 ℃/min, then the temperature is kept for 1h, then the temperature is reduced to the room temperature along with the furnace, and the sample is taken out.
After the silicon rubber sample is treated at 1000 ℃, the mass residual rate W of the silicon rubber samplerAnd the linear shrinkage S are calculated according to the formulae (1) and (2), respectively, in which m is1、m2Respectively represents the mass of the sample before and after high-temperature treatment, l1、l2The lengths of the samples before and after the high-temperature treatment are respectively represented as follows:
Wr＝(m2/m1)×100％ (1)
S＝(l1-l2)/l1×100％ (2)
after the high-temperature treatment, the organic-inorganic conversion (Rc) of the silicone rubber matrix in the sample was calculated according to the formula (3):
Rc＝[Wr-(97.6％×Qf+95.1％×Qs)]/[1.0-(Qf+Qs)]×100％ (3)
in the formula QfAnd QsRespectively represents the mass fractions of fluorophlogopite and fumed silica in the silicone rubber. In order to eliminate the partial weight loss of R in the process of treating fluorophlogopite and white carbon black at 1000 DEG CcThe fluorophlogopite and the fumed silica are independently treated according to the method and the conditions for treating the silicon rubber sample, and the mass residual rates of the fluorophlogopite and the fumed silica are 97.6 percent and 95.1 percent respectively.
TABLE 1 mechanical Properties of the Silicone rubbers
TABLE 2 flame retardancy and ceramifying Properties of Silicone rubber
As can be seen from Table 1, examples 1 to 5 all maintained good mechanical properties as compared with comparative examples 1 to 3. As can be seen from Table 2, the LOI of comparative example 1 was only 27.5%, the sample failed the vertical burning test, the organic-inorganic conversion of the silicone rubber matrix was only 2.7% after 1h of 1000 deg.C treatment (Table 2), a continuous and intact ceramic body was not formed (FIG. 3), and the ceramic body had a fluffy porous structure (FIG. 5). In comparison with comparative example 1, LOI of comparative example 2 in which fluorophlogopite alone was added was increased to 31.5%, and the three-point bending strength was 2.1 MPa. The laminar structure of the fluorophlogopite has the physical barrier effect and the framework supporting effect, so that the mass and heat transfer process of the silicon rubber during combustion can be prevented, and the silicon rubber is endowed with better porcelain forming performance at high temperature, so that the LOI and the three-point bending strength of the silicon rubber are improved, and the linear shrinkage rate is only 10.0%. But comparative example 2 still failed the vertical burn test. The LOI of comparative example 3 in which the divinyltetramethylsiloxane complex of chloroplatinic acid/γ -aminopropyltriethoxysilane was added was increased from 27.5% to 31.0%, the vertical burning grade reached V-1, and the mass residue rate after treatment at 1000 ℃ for 1 hour was increased to 40.1%, wherein the organic-inorganic conversion rate of the silicone rubber matrix was 20.2%. The platinum complex/nitrogen-containing silane system can promote the molecular chain of the silicon rubber to form a cross-linking structure at high temperature, so that the organic-inorganic conversion rate of the silicon rubber matrix is improved, and the flame retardant property of the silicon rubber is favorably improved. But the ceramifying property of comparative example 3 was not significantly improved.
Compared with comparative examples 1 to 3, the LOI of examples 1 to 5, in which fluorophlogopite and the platinum compound/nitrogen-containing silane system were added simultaneously, was more than 33.0%, and the highest was 37.5%, the vertical burning level was V-0, the mass residue rate and the matrix organic-inorganic conversion rate were further improved, the highest values were 56.7% and 28.2%, the three-point bending strength was more than 10.0MPa, the highest was 14.4MPa, and the linear shrinkage rate was maintained at about 9.0% (Table 2). In which example 1 self-extinguished within 6s after being ignited, exhibiting excellent flame retardant properties (fig. 2), and example 1 formed a fully dense ceramic body after 1h of treatment at 1000 c (fig. 4 and 6). This is a result of the interaction of fluorophlogopite and the platinum compound/nitrogen-containing silane system. On one hand, the fluorophlogopite has physical barrier effect and skeleton supporting effect, effectively prevents the mass transfer and heat transfer processes during the combustion of the silicon rubber, and improves the vitrification performance; on the other hand, the platinum compound/nitrogenous silane system promotes more silicone rubber molecular chains to form a cross-linked structure at high temperature, so that organic-inorganic conversion of the silicone rubber matrix is realized, a dense ceramic structure is formed together with fluorophlogopite and white carbon black, and the flame retardant property and the vitrification property are further improved. Therefore, the invention can realize excellent vitrification performance and flame retardant performance without adding traditional fluxing agents such as low-melting-point glass powder and the like and traditional flame retardants such as aluminum hydroxide, magnesium hydroxide, phosphorus and the like, effectively avoids the influence of a large amount of added low-melting-point fluxing agents and traditional flame retardants on the performance of the silicon rubber, and ensures that the silicon rubber still maintains good mechanical property and processability.
It should be noted that those skilled in the art to which the invention pertains will appreciate that alternative or obvious modifications of the embodiments described herein may be made without departing from the spirit of the invention, and such modifications are to be considered as falling within the scope of the invention.
Claims (8)
1. The porcelainized halogen-free flame-retardant silicone rubber is characterized by comprising the following raw materials in parts by mass:
a. methyl vinyl silicone rubber 100 parts
b. 30-50 parts of fumed silica
c. 30-50 parts of fluorophlogopite
d. 10-30 ppm of platinum compound calculated according to mass concentration of platinum in silicone rubber
e. 1-3 parts of nitrogenous silane
f. 4-8 parts of hydroxyl silicone oil
g. 0.4 to 0.8 portion of hydrogen-containing silicone oil
h. 1.5-2.5 parts of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide
The nitrogenous silane is N-phenyl-3-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-piperazinylpropylmethyldimethoxysilane or gamma-ureidopropyltrimethoxysilane;
the porcelainized halogen-free flame-retardant silicone rubber is prepared by the following steps:
(1) putting methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and hydrogen-containing silicone oil into a kneading machine together, mixing for 1-2 h, heating to 140-160 ℃, continuing mixing for 2-4 h, then vacuumizing and mixing for 0.5-1.5 h at 120-130 ℃, mixing uniformly, and cooling to room temperature to obtain base rubber;
(2) uniformly mixing the base rubber obtained in the step (1), fluorophlogopite, a platinum compound and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide on a double-roll mill; and vulcanizing at 160-170 ℃ for 15-30 min, and vulcanizing for two stages at 180-200 ℃ for 1-2 h to obtain the silicone rubber.
2. The ceramifiable halogen-free flame-retardant silicone rubber according to claim 1, wherein the methyl vinyl silicone rubber is two kinds of methyl vinyl silicone rubber with vinyl contents of 0.05mol% to 0.10mol% and 2.0mol% to 4.0mol%, and the mass ratio of the former to the latter is 98: 2-90: 10, the molecular weight of both is 500000-700000 g/mol.
3. The ceramifiable halogen-free flame-retardant silicone rubber according to claim 1, wherein the fumed silica has a specific surface area of 200-300 m2/g。
4. The ceramifiable halogen-free flame-retardant silicone rubber according to claim 1, wherein the fluorophlogopite has a particle size of 800-3000 mesh.
5. The ceramifiable halogen-free flame-retardant silicone rubber according to claim 1, wherein the platinum compound is one of an isopropanol solution of chloroplatinic acid, a tetrahydrofuran solution of chloroplatinic acid, and a divinyltetramethyldisiloxane complex of chloroplatinic acid.
6. The ceramifiable halogen-free flame-retardant silicone rubber according to claim 1, wherein the hydroxyl group content of the hydroxyl silicone oil is 5wt% to 10 wt%.
7. The ceramifiable halogen-free flame-retardant silicone rubber according to claim 1, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.0wt% to 1.5 wt%.
8. The method for preparing the ceramifiable halogen-free flame-retardant silicone rubber according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) putting methyl vinyl silicone rubber, fumed silica, hydroxyl silicone oil and hydrogen-containing silicone oil into a kneading machine together, mixing for 1-2 h, heating to 140-160 ℃, continuing mixing for 2-4 h, then vacuumizing and mixing for 0.5-1.5 h at 120-130 ℃, mixing uniformly, and cooling to room temperature to obtain base rubber;
(2) uniformly mixing the base rubber obtained in the step (1), fluorophlogopite, a platinum compound and 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide on a double-roll mill; and vulcanizing at 160-170 ℃ for 15-30 min, and vulcanizing for two stages at 180-200 ℃ for 1-2 h to obtain the silicone rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911083874.7A CN110845850B (en) | 2019-11-07 | 2019-11-07 | Ceramizable halogen-free flame-retardant silicone rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911083874.7A CN110845850B (en) | 2019-11-07 | 2019-11-07 | Ceramizable halogen-free flame-retardant silicone rubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110845850A CN110845850A (en) | 2020-02-28 |
| CN110845850B true CN110845850B (en) | 2020-10-27 |
Family
ID=69598976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911083874.7A Active CN110845850B (en) | 2019-11-07 | 2019-11-07 | Ceramizable halogen-free flame-retardant silicone rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110845850B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592763B (en) * | 2020-05-25 | 2022-03-08 | 深圳市莱美斯硅业有限公司 | Fireproof silica gel cloth and preparation method and application thereof |
| CN112280310A (en) * | 2020-10-21 | 2021-01-29 | 佛山科学技术学院 | Halogen-free flame-retardant silicone rubber and preparation method and application thereof |
| CN112375389A (en) * | 2020-10-21 | 2021-02-19 | 佛山科学技术学院 | High-temperature-resistant silicon rubber and preparation method and application thereof |
| CN113308120B (en) * | 2021-06-30 | 2022-05-24 | 华南理工大学 | Light ceramizable silicone rubber and preparation method thereof |
| CN115538175B (en) | 2022-10-18 | 2024-02-02 | 浙江葆润应用材料有限公司 | Flame-retardant heat-insulating fireproof material for battery |
| CN117417638A (en) * | 2023-10-17 | 2024-01-19 | 合肥华城材料科技有限责任公司 | High-temperature-resistant flame-retardant mica composite organic silicon rubber and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774474A (en) * | 2015-01-04 | 2015-07-15 | 华南理工大学 | Halogen-free flame-retardant reinforced addition liquid silicone rubber and preparation method thereof |
| WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
| CN108219473A (en) * | 2017-09-07 | 2018-06-29 | 北京化工大学 | Room temperature vulcanization Ceramic silicon rubber foam seal agent and preparation method thereof |
| CN108587181A (en) * | 2018-03-21 | 2018-09-28 | 上海大学 | One kind can porcelain SiClx rubber thermally protective materials and preparation method thereof |
| CN109054395A (en) * | 2018-06-27 | 2018-12-21 | 华南理工大学 | A kind of high temperature resistant halogen-free flame-retardant silicon rubber and preparation method thereof |
-
2019
- 2019-11-07 CN CN201911083874.7A patent/CN110845850B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774474A (en) * | 2015-01-04 | 2015-07-15 | 华南理工大学 | Halogen-free flame-retardant reinforced addition liquid silicone rubber and preparation method thereof |
| WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
| CN108219473A (en) * | 2017-09-07 | 2018-06-29 | 北京化工大学 | Room temperature vulcanization Ceramic silicon rubber foam seal agent and preparation method thereof |
| CN108587181A (en) * | 2018-03-21 | 2018-09-28 | 上海大学 | One kind can porcelain SiClx rubber thermally protective materials and preparation method thereof |
| CN109054395A (en) * | 2018-06-27 | 2018-12-21 | 华南理工大学 | A kind of high temperature resistant halogen-free flame-retardant silicon rubber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Platinum loaded cyclomatrix polyphosphazene submicrospheres improve;Xiaodong Guo, Xiaowei Geng, Xiangdi Gao，et al.;《Composites Communications》;20181015;全文 * |
| Synergistic effect and mechanism of platinum catalyst andnitrogen-containing silane on the thermal stability of silicone rubber;rubberWanjuan Chen, Xingrong Zeng，Xuejun Lai,et al.;《Thermochimica Acta》;20160315;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110845850A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110845850B (en) | Ceramizable halogen-free flame-retardant silicone rubber and preparation method thereof | |
| CN111303636B (en) | Low-heat-conductivity flame-retardant fireproof silicone rubber composite material and preparation method thereof | |
| JP6617983B2 (en) | Ceramicized silicone resin composition, and prepreg and laminate using the same | |
| Hamdani et al. | Flame retardancy of silicone-based materials | |
| CN107163585B (en) | It is a kind of can low-temp ceramics silicon rubber and preparation method thereof | |
| CN107286636B (en) | Low-smoke flame-retardant ceramic thermoplastic polyurethane elastomer composite material and preparation method and application thereof | |
| JPS60179436A (en) | Flame-retarding polyolefin rubber composition | |
| CN103739927B (en) | Temperature resistant grade is low-smoke zero-halogen cable material formula and the preparation method of 150 DEG C | |
| CN111004511A (en) | High-strength high-temperature-resistant flame-retardant silicone rubber and preparation method thereof | |
| JPH0113730B2 (en) | ||
| CN112745571B (en) | Antimony-free flame-retardant ceramic polyolefin composition and preparation method and application thereof | |
| CN110128831A (en) | It is a kind of with excellent at porcelain and the Ceramic silicon rubber of anti-flammability and the preparation method and application thereof | |
| CN109824974A (en) | A kind of halogen-free flame-retardant composite material and preparation method thereof of high flowing antibacterial | |
| Wang et al. | Significantly improve fire safety of silicone rubber by efficiently catalyzing ceramization on fluorophlogopite | |
| CN113308120B (en) | Light ceramizable silicone rubber and preparation method thereof | |
| CN110229526B (en) | High-temperature-resistant ceramic silicone rubber and preparation method and application thereof | |
| CN111471304A (en) | Flame-retardant and fire-resistant silicon rubber material and preparation method and application thereof | |
| CN113278289B (en) | Flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof | |
| CN113881230A (en) | Ceramic silicone rubber for heat insulation of power battery and preparation method thereof | |
| CN108912691A (en) | A kind of low loading halogen-free anti-flaming silicon rubber and preparation method thereof | |
| CN112094502A (en) | High-temperature-resistant mixed silicone rubber and preparation method thereof | |
| CN114605839B (en) | Ceramic silicon rubber with obvious XRD new crystallization peak after calcination and preparation method thereof | |
| CN114231040B (en) | Flame-retardant silicone rubber self-adhesive tape and preparation method thereof | |
| CN112920461B (en) | Ceramic filler, preparation method thereof and EPDM (ethylene-propylene-diene monomer) composite material | |
| JP3114524B2 (en) | Flame retardant resin composition |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |