CN116120753A - Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof - Google Patents
Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof Download PDFInfo
- Publication number
- CN116120753A CN116120753A CN202310020397.XA CN202310020397A CN116120753A CN 116120753 A CN116120753 A CN 116120753A CN 202310020397 A CN202310020397 A CN 202310020397A CN 116120753 A CN116120753 A CN 116120753A
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- flame
- cage
- retardant
- type silsesquioxane
- 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
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 85
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 66
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000919 ceramic Substances 0.000 title claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 28
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims abstract description 6
- 238000004891 communication Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical group C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000010074 rubber mixing Methods 0.000 claims description 7
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 230000005684 electric field Effects 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002468 ceramisation Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000861 blow drying Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OGNSDRMLWYNUED-UHFFFAOYSA-N 1-cyclohexyl-4-[4-[4-(4-cyclohexylcyclohexyl)cyclohexyl]cyclohexyl]cyclohexane Chemical group C1CCCCC1C1CCC(C2CCC(CC2)C2CCC(CC2)C2CCC(CC2)C2CCCCC2)CC1 OGNSDRMLWYNUED-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229960004365 benzoic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ARLJCLKHRZGWGL-UHFFFAOYSA-N ethenylsilicon Chemical compound [Si]C=C ARLJCLKHRZGWGL-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iron-magnesium-aluminum Chemical compound 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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 belongs to the field of flame-retardant silicone rubber, and discloses flame-retardant silicone rubber with good thermal stability, high carbon residue and easy ceramization at high temperature, and a preparation method and application thereof. The silicone rubber is mainly prepared from the following raw materials in parts by weight: vinyl silicone rubber, hydrogen-containing silicone oil crosslinking agent, platinum catalyst, flame retardant and glass powder. The flame retardant is a layered metal hydroxide modified by cage silsesquioxane. The silicon rubber prepared by the invention can be applied to specific fields such as new energy automobile battery pack materials, communication industry and the like.
Description
Technical Field
The invention belongs to the field of flame-retardant silicone rubber, and particularly relates to flame-retardant silicone rubber with good thermal stability, high carbon residue and easy ceramization at high temperature, and a preparation method and application thereof.
Background
With the development of technology, new energy automobiles occupy more and more proportion, but the safety of the new energy automobile battery pack materials is still a great challenge. In order to improve the safety performance thereof, silicone rubber may be used as a material of the battery pack because silicone rubber has good thermal stability, excellent fire resistance, and electrical insulation. However, silicone rubber burns continuously once it is ignited, and the residue after combustion has little mechanical strength. In order to solve the problem, a silicone rubber with flame retardant effect and easy porcelain formation is needed to be prepared.
The flame retardant property and the porcelain forming property of the silicone rubber are improved, and a flame retardant and a fluxing agent are generally added into the silicone rubber. The flame retardant which is more commonly used at present is Al (OH) 3 And Mg (OH) 2 The preparation method has the advantages of low price, no toxicity, smoke suppression, good thermal stability and the like, but the problems of low decomposition temperature, agglomeration and the like limit the wide application of the preparation method. The invention uses the iron-magnesium-aluminum ternary layered metal hydroxide (LDH) as a flame retardant, which has Al (OH) at the same time 3 And Mg (OH) 2 And the material is heated to decompose and release a large amount of water and carbon dioxide, so that the flame retardance and the thermal stability of the material can be improved. However, LDHs have problems such as poor compatibility with matrix materials and poor flame retardant efficiency, and further improvement of LDHs is still needed to solve the problems. And the fluxing agent is added into the silicon rubber, so that a compact protective layer can be formed at high temperature, flame is isolated, electrolyte leakage is prevented, and the safety performance of the battery pack material is improved.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the primary purpose of the invention is to provide the easily-ceramic flame-retardant silicone rubber; the silicone rubber is high in thermal stability and carbon residue and Wen Yicheng porcelain, and is prepared from flame retardant and glass powder of cage-type silsesquioxane modified layered metal compound (LDH-SQ) containing carboxylic acid structure.
The invention also aims to provide a preparation method of the easy-ceramization flame-retardant silicone rubber; according to the method, cage-type silsesquioxane modified FeMgAl-LDH containing vinyl, benzene carboxylic acid and polyethylene glycol structure can be used as a flame-retardant and porcelain-forming auxiliary agent and low-melting-point glass powder to prepare flame-retardant and porcelain-forming silicone rubber; the cage-type silsesquioxane used as the modifier has the advantages of high thermal stability and good compatibility with silicon rubber, and the vinyl in the cage-type silsesquioxane structure can be subjected to crosslinking reaction with vinyl silicon rubber or a hydrogen-containing crosslinking agent in the vulcanization process, so that the binding force of LDH and the silicon rubber is improved, and the compatibility of the silicon rubber is further improved.
The aim of the invention is achieved by the following technical scheme:
the easy-to-ceramic flame-retardant silicone rubber is prepared from the following raw materials in parts by weight: 100 parts of silicone rubber, 0.5-2 parts of hydrogen-containing silicone oil crosslinking agent, 0.1-1 part of platinum catalyst, 10-30 parts of cage-type silsesquioxane modified layered metal hydroxide flame retardant (LDH-SQ) and 10-30 parts of low-temperature glass powder.
The silicon rubber is methyl vinyl silicon rubber, and the vinyl content is 0.1-1 mol%.
The melting point of the glass powder is 300-600 ℃.
The cage type silsesquioxane modified layered metal hydroxide flame retardant is prepared by the following steps:
s1, preparing vinyl and phenyl-containing cage-type Silsesquioxane (SQ) by using vinyl triethoxysilane and phenyl triethoxysilane through a silane hydrolysis method; then clicking the sulfhydryl-containing polyethylene glycol on a double bond structure of cage-type Silsesquioxane (SQ) containing vinyl and phenyl through a clicking reaction, and then reacting the phenyl into a benzene carboxylic acid structure through a Friedel-crafts acylation reaction to finally obtain the cage-type silsesquioxane connected with vinyl, polyethylene glycol and anionic groups;
s2, obtaining a cage-type silsesquioxane modified layered metal hydroxide flame retardant (LDH-SQ) through a coprecipitation method by using the cage-type silsesquioxane connected with vinyl, polyethylene glycol and anionic groups, sodium hydroxide solution and salt solution obtained in the step S1; the salt solution is a solution of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and ferric nitrate nonahydrate.
The molecular weight range of the sulfhydryl-containing polyethylene glycol in the step S1 is 200-1000 Da; the particle size of the cage type silsesquioxane modified layered metal hydroxide flame retardant obtained in the step S2 is 200-600 meshes.
More preferably, the molecular weight of the sulfhydryl-containing polyethylene glycol in the step S1 ranges from 200 Da to 500Da; the particle size of the cage type silsesquioxane modified layered metal hydroxide flame retardant obtained in the step S2 is 400 meshes.
The preparation method of the easy-to-ceramic flame-retardant silicone rubber comprises the following operation steps: processing silicon rubber on an open double-roller rubber mixing mill, sequentially adding a cage-type silsesquioxane modified layered metal hydroxide flame retardant and glass powder for uniform mixing after a rubber sheet is wrapped, sequentially adding a hydrogen-containing silicone oil cross-linking agent and a platinum catalyst for uniform mixing, and carrying out thin communication; finally, vulcanizing at a high temperature to obtain the easy-to-ceramic flame-retardant silicone rubber.
The temperature of the mixing is 30-50 ℃.
The high-temperature vulcanization temperature is 100-200 ℃, and the vulcanization time is 2-4 h.
The easy-to-ceramic flame-retardant silicone rubber can be applied to the fields of new energy automobile battery pack materials, communication fields, electronics and electrical fields, buildings, transmission lines and the like.
The principle of the invention is as follows:
the cage-type silsesquioxane modified layered metal hydroxide flame retardant is a modified layered metal hydroxide (LDH-SQ), and can be converted from hydrophilic performance to hydrophobic performance, so that the compatibility of the layered metal hydroxide (LDH) and silicone rubber can be improved. The double bond structure in the cage silsesquioxane can further react with vinyl silicone rubber or hydrogen-containing silicone oil crosslinking agent in the vulcanization process, so that the binding force between LDH and a polymer matrix is improved, and the mechanical property of the material is improved. The magnesium oxide produced by high-temperature decomposition of LDH (containing Fe, mg and Al) is a very good fluxing agent, so that the strength and density of porcelain compounds are improved, and meanwhile, fe can be catalyzed into charcoal in the combustion process, and the carbonization of silicon rubber is promoted. The low-temperature glass powder can be melted to have eutectic reaction with alumina, silicon dioxide and the like, so as to promote the porcelain formation of the silicon rubber.
Compared with the prior art, the invention has the following advantages and effects:
(1) The preparation method is simple in preparation process, simple and convenient in post-treatment and operation.
(2) The invention comprehensively utilizes the common advantages of LDH, SQ and glass powder to improve the flame retardance and porcelain forming performance of the silicone rubber.
Drawings
FIG. 1 shows the structural formula of cage type silsesquioxane obtained in example 1.
FIG. 2 shows the nuclear magnetic resonance spectrum of the cage-type silsesquioxane obtained in example 1.
FIG. 3 is a thermal weight spectrum of the modified silicone rubber obtained in example 2.
FIG. 4 is a micro calorimetric diagram of the modified silicone rubber obtained in example 2.
FIG. 5 is a scanning electron microscope spectrum of the modified silicone rubber obtained in example 3 after calcination.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention.
EXAMPLE 1 preparation of modified LDH
(1) 10mmol of vinyltriethoxysilane was added dropwise to a solution containing 10mmol of potassium methoxide, 9ml of isopropanol and 2g of deionized water using a constant pressure funnel, and tetravinylsiloxane was obtained by a silane hydrolysis reaction; tetravinyl siloxane (10 mmol) is reacted with phenyl triethoxysilane (60 mmol), potassium methoxide (60 mmol), catalyst tetramethyl ammonium fluoride (1 mmol) and tetrahydrofuran solvent (200 ml) through silane hydrolysis reaction to obtain tetravinyl hexaphenyl cage type silsesquioxane; finally, polyethylene glycol with the average molecular weight of 350 is clicked to a double bond through a click reaction, and phenyl is subjected to Friedel-crafts acylation reaction to finally obtain the amphiphilic cage-type silsesquioxane, wherein the structural formula is shown in figure 1, the nuclear magnetic hydrogen spectrum is shown in figure 2, and the successful preparation of the amphiphilic cage-type silsesquioxane is proved.
(2) The amphiphilic cage type silsesquioxane (1.0 mmol) obtained in the step (1) is dissolved in tetrahydrofuran and an aqueous solution, the pH=10 is adjusted, meanwhile, a salt solution (the salt solution contains magnesium nitrate hexahydrate (5.4 mmol), aluminum nitrate nonahydrate (3.0 mmol) and ferric nitrate nonahydrate (0.6 mmol)) and a 1.0mol/L sodium hydroxide solution are respectively added dropwise, the pH=10 is kept in the whole dropwise adding process, and the mixture is stirred for 1h and reacts for 18h at 90 ℃ to obtain the modified layered metal hydroxide (LDH-SQ).
Example 2
The above-mentioned modified layered metal hydroxide (LDH-SQ) and low-temperature glass frit were replaced with only layered metal hydroxide (LDH), and the other steps were the same, and the prepared silicone rubber was used as a control group.
The thermogravimetric spectrum of the obtained sample is shown in fig. 3, and it can be seen that the thermal stability of the silicon rubber added with only unmodified LDH is lower than that of the silicon rubber added with modified LDH-SQ and low-temperature glass powder at 450 ℃, and the carbon residue rate is improved by 36%. The micro calorimetric spectrum of the obtained sample is shown in fig. 4, and it can be seen that the Heat Release Rate (HRR) of the modified LDH-SQ and the low-temperature glass powder silicon rubber at 450 ℃ is obviously reduced, and the purpose of delaying combustion is achieved to improve the flame retardance.
Example 3
The above-mentioned modified layered metal hydroxide (LDH-SQ) and low-temperature glass frit were replaced with only layered metal hydroxide (LDH), and the other steps were the same, and the prepared silicone rubber was used as a control group.
And (3) placing the obtained silicon rubber in a muffle furnace to calcine at 400 ℃ for 3 hours to obtain silicon rubber residues. The scanning electron microscope spectrum of the calcined silicone rubber residue is shown in fig. 5, and it can be seen that the surface of the calcined control silicone rubber only added with unmodified LDH has obvious cracks, further combustion cannot be prevented, the silicone rubber added with modified layered metal hydroxide LDH-SQ and low-temperature glass powder has no cracks, and compared with the control silicone rubber only added with unmodified LDH, the C and Si elements migrate to the surface, so that the formation of a barrier layer is promoted, further combustion is prevented, and the purpose of flame retardance is achieved.
Example 4
100 parts by weight of methyl vinyl silicone rubber (with 0.5mol% of vinyl content) is processed on an open double-roll rubber mixing mill, 20 parts by weight of the modified layered metal hydroxide flame retardant obtained in the example 1 are sequentially added after the silicone rubber is wrapped, 20 parts by weight of low-temperature glass powder (with the melting point of 500 ℃) are sequentially mixed uniformly at normal temperature, then 2 parts by weight of platinum cross-linking agent and 0.5 part by weight of platinum catalyst are sequentially added for mixing uniformly for about 25 minutes, and a film with the thickness of 3mm is finally obtained after 6 times of thin pass. Subsequently, the film was vulcanized in a blow-drying oven at 150℃for 3 hours to obtain a smooth and flat modified silicone rubber (i.e., a flame-retardant silicone rubber which was liable to ceramization).
Example 5
100 parts by weight of methyl vinyl silicone rubber (with 0.5mol% of vinyl content) is processed on an open double-roll rubber mixing mill, 30 parts by weight of the modified layered metal hydroxide flame retardant obtained in the example 1 and 30 parts by weight of low-temperature glass powder (with the melting point of 400 ℃) are sequentially added after the silicone rubber is wrapped and rolled, a platinum cross-linking agent (2 parts by weight) and a platinum catalyst (1 part by weight) are sequentially added after the mixture is uniformly mixed at normal temperature, the mixture is uniformly mixed for about 25 minutes, and the mixture is thinned and passed for 6 times, so that a film with the thickness of 3mm is finally obtained. Subsequently, the film was vulcanized in a blow-drying oven at 150℃for 3 hours to obtain a smooth and flat modified silicone rubber (i.e., a flame-retardant silicone rubber which was liable to ceramization).
Example 6
100 parts by weight of methyl vinyl silicone rubber (with 0.14mol% of vinyl content) is processed on an open double-roll rubber mixing mill, 15 parts by weight of modified Layered Metal Hydroxide (LMHs) flame retardant obtained in example 1 is sequentially added after the silicone rubber is wrapped, 30 parts by weight of low-temperature glass powder (melting point 500 ℃) is uniformly mixed at normal temperature, then a platinum cross-linking agent (1 part by weight) and a platinum catalyst (0.5 part by weight) are sequentially added, the mixture is uniformly mixed for about 25 minutes, the mixture is thinned and passed for 6 times, and finally a film with the thickness of 3mm is obtained. Subsequently, the film was vulcanized in a blow-drying oven at 180℃for 2 hours to obtain a smooth and flat modified silicone rubber (i.e., a flame-retardant silicone rubber which was liable to ceramization).
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. An easy-to-ceramic flame-retardant silicone rubber, which is characterized in that: the silicone rubber is prepared from the following raw materials in parts by weight: 100 parts of silicone rubber, 0.5-2 parts of hydrogen-containing silicone oil crosslinking agent, 0.1-1 part of platinum catalyst, 10-30 parts of cage-type silsesquioxane modified layered metal hydroxide flame retardant and 10-30 parts of glass powder.
2. The ceramic-prone flame-retardant silicone rubber according to claim 1, wherein: the silicon rubber is methyl vinyl silicon rubber, and the vinyl content is 0.1-1 mol%.
3. The ceramic-prone flame-retardant silicone rubber according to claim 1, wherein: the melting point of the glass powder is 300-600 ℃.
4. The ceramic-prone flame-retardant silicone rubber according to claim 1, wherein: the cage type silsesquioxane modified layered metal hydroxide flame retardant is prepared by the following steps:
s1, preparing vinyl and phenyl-containing cage-type silsesquioxane by using vinyl triethoxysilane and phenyl triethoxysilane through a silane hydrolysis method; then clicking the sulfhydryl-containing polyethylene glycol on the double bond structure of the cage-type silsesquioxane containing vinyl and phenyl through a clicking reaction, and then reacting the phenyl into a benzene carboxylic acid structure through a Friedel-crafts acylation reaction to finally obtain the cage-type silsesquioxane connected with vinyl, polyethylene glycol and anionic groups;
s2, the cage-type silsesquioxane which is connected with vinyl, polyethylene glycol and anionic groups and obtained in the step S1, sodium hydroxide solution and salt solution are subjected to a coprecipitation method to obtain a cage-type silsesquioxane modified layered metal hydroxide flame retardant; the salt solution is a solution of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and ferric nitrate nonahydrate.
5. The ceramic-easy flame retardant silicone rubber according to claim 4, wherein: the molecular weight range of the sulfhydryl-containing polyethylene glycol in the step S1 is 200-1000 Da; the particle size of the cage type silsesquioxane modified layered metal hydroxide flame retardant obtained in the step S2 is 200-600 meshes.
6. The ceramic-easy flame retardant silicone rubber according to claim 4, wherein: the molecular weight range of the sulfhydryl-containing polyethylene glycol in the step S1 is 200-500 Da; the particle size of the cage type silsesquioxane modified layered metal hydroxide flame retardant obtained in the step S2 is 400 meshes.
7. The preparation method of the easy-to-ceramic flame-retardant silicone rubber according to claim 1, which is characterized by comprising the following operation steps: processing silicon rubber on an open double-roller rubber mixing mill, sequentially adding a cage-type silsesquioxane modified layered metal hydroxide flame retardant and glass powder for uniform mixing after a rubber sheet is wrapped, sequentially adding a hydrogen-containing silicone oil cross-linking agent and a platinum catalyst for uniform mixing, and carrying out thin communication; finally, vulcanizing at a high temperature to obtain the easy-to-ceramic flame-retardant silicone rubber.
8. The method of manufacturing according to claim 7, wherein: the temperature of the mixing is 30-50 ℃.
9. The method of manufacturing according to claim 7, wherein: the high-temperature vulcanization temperature is 100-200 ℃, and the vulcanization time is 2-4 h.
10. The application of the easy-to-ceramic flame-retardant silicone rubber according to claim 1 in the fields of new energy automobile battery pack materials, communication fields, electronics and electrical fields, buildings and transmission lines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310020397.XA CN116120753A (en) | 2023-01-06 | 2023-01-06 | Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310020397.XA CN116120753A (en) | 2023-01-06 | 2023-01-06 | Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116120753A true CN116120753A (en) | 2023-05-16 |
Family
ID=86298734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310020397.XA Pending CN116120753A (en) | 2023-01-06 | 2023-01-06 | Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116120753A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275406A (en) * | 2013-05-21 | 2013-09-04 | 河海大学 | Halogen-free flame retardant polystyrene nano composite material and preparation method thereof |
| CN104829864A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of polyhedral oligomeric silsesquioxane-aluminum hydroxide composite flame-resistant material |
| CN104830067A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of a polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material |
| WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
| CN107760039A (en) * | 2017-11-02 | 2018-03-06 | 广东聚合科技股份有限公司 | A kind of ceramic flame-retardant silicon rubber and preparation method thereof |
| CN110105769A (en) * | 2019-05-08 | 2019-08-09 | 山东百多安医疗器械有限公司 | A kind of high-mechanical property silicon rubber and preparation method thereof of POSS enhancing |
| CN110128831A (en) * | 2019-04-29 | 2019-08-16 | 华南理工大学 | It is a kind of with excellent at porcelain and the Ceramic silicon rubber of anti-flammability and the preparation method and application thereof |
| CN114231041A (en) * | 2021-12-31 | 2022-03-25 | 上海电缆研究所有限公司 | B1-grade flame-retardant ceramic low-smoke silicone rubber cable material and preparation method thereof |
| KR20220061303A (en) * | 2020-11-05 | 2022-05-13 | 한국철도기술연구원 | Low specific gravity flame-retardant silicone rubber and preparation method thereof |
| WO2022135250A1 (en) * | 2020-12-21 | 2022-06-30 | 金发科技股份有限公司 | Alloy material having ceramicized surface, preparation method therefor and application thereof |
-
2023
- 2023-01-06 CN CN202310020397.XA patent/CN116120753A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275406A (en) * | 2013-05-21 | 2013-09-04 | 河海大学 | Halogen-free flame retardant polystyrene nano composite material and preparation method thereof |
| CN104829864A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of polyhedral oligomeric silsesquioxane-aluminum hydroxide composite flame-resistant material |
| CN104830067A (en) * | 2015-05-08 | 2015-08-12 | 广西经正科技开发有限责任公司 | Preparation method of a polyhedral oligomeric silsesquioxane-magnesium hydroxide composite flame-resistant material |
| WO2017070893A1 (en) * | 2015-10-29 | 2017-05-04 | 国家纳米科学中心 | Ceramic silicone rubber, preparation method and use thereof |
| CN107760039A (en) * | 2017-11-02 | 2018-03-06 | 广东聚合科技股份有限公司 | A kind of ceramic flame-retardant silicon rubber and preparation method thereof |
| CN110128831A (en) * | 2019-04-29 | 2019-08-16 | 华南理工大学 | It is a kind of with excellent at porcelain and the Ceramic silicon rubber of anti-flammability and the preparation method and application thereof |
| CN110105769A (en) * | 2019-05-08 | 2019-08-09 | 山东百多安医疗器械有限公司 | A kind of high-mechanical property silicon rubber and preparation method thereof of POSS enhancing |
| KR20220061303A (en) * | 2020-11-05 | 2022-05-13 | 한국철도기술연구원 | Low specific gravity flame-retardant silicone rubber and preparation method thereof |
| WO2022135250A1 (en) * | 2020-12-21 | 2022-06-30 | 金发科技股份有限公司 | Alloy material having ceramicized surface, preparation method therefor and application thereof |
| CN114231041A (en) * | 2021-12-31 | 2022-03-25 | 上海电缆研究所有限公司 | B1-grade flame-retardant ceramic low-smoke silicone rubber cable material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112745610A (en) | Modified Mxene/PVA flame-retardant composite material and preparation method thereof | |
| CN105885197B (en) | Flame-retardant ceramic EVA and preparation method thereof | |
| CN113980551B (en) | Hydrotalcite-based water-based epoxy resin intumescent fire-retardant coating | |
| CN113817287A (en) | Bio-based nano synergistic flame retardant and preparation method and application thereof | |
| CN112175575A (en) | Preparation method of industrial silicone sealant | |
| CN116120753A (en) | Easily-ceramic flame-retardant silicone rubber and preparation method and application thereof | |
| CN115028864B (en) | Element-doped BCZT/PVDF core-shell material, flexible film, preparation method and capacitor | |
| CN112501921A (en) | Organic silicon coating and preparation method thereof | |
| CN109354878B (en) | Organic ceramic precursor modified bimetallic hydroxide nanosheet and preparation method and application thereof | |
| CN115160575B (en) | Flame-retardant ethylene propylene diene monomer rubber and preparation method thereof | |
| CN115948002A (en) | Flame-retardant rubber material, preparation method thereof and sealing strip | |
| CN114395167A (en) | Carbon microsphere @ hydrotalcite @ polyphosphazene hybrid flame retardant and preparation method thereof | |
| CN114409277B (en) | Low-radiation LOW-E hollow glass | |
| CN110183644A (en) | A kind of preparation method of graphene oxide modified flame-retardant polyalcohol | |
| CN115717052A (en) | Graphene modified single-component sealant capable of resisting high temperature for long time and preparation method and application thereof | |
| CN112300445B (en) | Ceramic refractory filler and preparation method and application thereof | |
| CN115028838B (en) | Nano-doped cage-type octaphenyl silsesquioxane, and preparation method and application thereof | |
| CN115594979B (en) | Flame-retardant and tracking-resistant silicone rubber composition and preparation method and application thereof | |
| CN114591589B (en) | Styrene elastomer for new energy charging pile cable and preparation method thereof | |
| CN117987064B (en) | High-limit modified bi-component heat-conducting adhesive for power battery and preparation method thereof | |
| CN117525554A (en) | Surface modification method of garnet-type solid electrolyte | |
| CN117402496A (en) | High-flame-retardance rapid ceramic silicon rubber and preparation method thereof | |
| KR101039007B1 (en) | Aluminum hydroxide Particle Improving for Fire-retardant and Production Method Thereof | |
| CN113131090A (en) | Diaphragm coating material, diaphragm, preparation method of diaphragm and battery cell | |
| CN114957852A (en) | 5G communication cable insulating layer material with printing migration resistance and flame retardant function and preparation method thereof |
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 |