CN115124764A - Flame-retardant heat-conducting agent for silicone rubber and preparation method thereof - Google Patents
Flame-retardant heat-conducting agent for silicone rubber and preparation method thereof Download PDFInfo
- Publication number
- CN115124764A CN115124764A CN202210656420.XA CN202210656420A CN115124764A CN 115124764 A CN115124764 A CN 115124764A CN 202210656420 A CN202210656420 A CN 202210656420A CN 115124764 A CN115124764 A CN 115124764A
- Authority
- CN
- China
- Prior art keywords
- flame
- retardant
- silicone rubber
- heat
- carbon nano
- 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
- 239000003063 flame retardant Substances 0.000 title claims abstract description 60
- 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 57
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 54
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 32
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 229910003153 β-FeOOH Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000004073 vulcanization Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000013040 rubber vulcanization Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- -1 hydroxyl ferric oxide Chemical compound 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000009891 weiqi Substances 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
Abstract
The invention relates to the technical field of flame-retardant heat conduction, in particular to a flame-retardant heat-conducting agent for silicon rubber. The invention also relates to a preparation method of the flame-retardant heat-conducting agent. According to the scheme, the flame-retardant heat-conducting agent can enhance the strength and compactness of a brittle carbon layer generated in the silicone rubber combustion process, and isolate heat transfer and exchange of combustible gas. In addition, the flame-retardant heat-conducting agent can also construct a three-dimensional structure in the silicon rubber, and the carbon nano tube provides rapid phonon conduction and improves the heat-conducting property of the material. On the surface of the carbon nano tube, the radial distribution of the hydroxyl ferric oxide nanocubes can effectively improve the heat conduction efficiency of the material. Meanwhile, the modification of the iron oxyhydroxide on the carbon nano tube improves the flame retardant effect of the carbon nano tube, and the surface modification of the silane coupling agent improves the dispersibility of the carbon nano tube in the silicone rubber.
Description
Technical Field
The invention relates to the technical field of flame-retardant heat conduction, in particular to a flame-retardant heat-conducting agent for silicone rubber and a preparation method thereof.
Background
Silicone rubber is one of important special silicone products, and is widely applied to the fields of sealing, insulation, wires and cables and the like. It is usually prepared from linear polysiloxane, cross-linking agent, reinforcing agent, and other additives. The Limiting Oxygen Index (LOI) of silicone rubber is high, but the silicone rubber is easily smoldering, and when exposed to open fire, the silicone rubber can continuously burn, and is inflammable. And the silicone rubber material is a poor conductor of heat, thus greatly limiting its application range.
Carbon Nanotubes (CNTs) are a class of one-dimensional carbon nanomaterials with excellent thermal, mechanical and electronic properties. The carbon nano tube can form a protective layer with a network structure in the combustion process, and can effectively improve the flame retardant property of the polymer when being used as a flame retardant. The carbon nano tube with high thermal conductivity can effectively improve the thermal conductivity of the polymer when being added into the polymer.
The iron oxyhydroxide is used as an inorganic flame retardant, does not generate toxic and corrosive gases, has high safety and is environment-friendly, but has limited flame retardant effect and is generally used together with other flame retardants.
Different flame retardants are loaded in a chemical grafting or electrostatic adsorption mode, and the like, so that the hybrid material can effectively improve the dispersion performance of the flame retardants in the composite material and improve the flame retardance of the composite material. Specifically, royal weiqi [ royal weiqi, ruby, panhaifeng, etc. Based on the flame retardant property research of binary hybrid of graphene oxide and carbon nano tube, industrial safety and environmental protection.2017, 43 (03): 33-37.]Graphene/carbon nanotube (CNT/GO) binary hybrids were prepared for coating into flexible polyurethane foam (RPUF) and the effect of GO, CNTs and CNT/GO on RPUF flame retardant performance was studied, showing that: heat of CNT/GO coated composites on top of 8 layers eachThe peak release rate (pHRR) and Total Heat Released (THR) are much lower than those of GO or CNT coated only, and are only 155.1 kW.m -2 And 16.0 MJ.m -2 。
Therefore, the present application is directed to the preparation of a flame-retardant heat-conductive agent having excellent effects suitable for silicone rubber.
Disclosure of Invention
The invention aims to provide a flame-retardant heat-conducting agent capable of effectively improving the flame retardance and the heat conductivity of silicone rubber and also capable of effectively improving the mechanical property of the silicone rubber.
In order to achieve the purpose, the invention adopts the technical scheme that: a flame-retardant heat-conducting agent for silicone rubber is characterized in that: generating iron oxyhydroxide on the surface of the carbon nano tube by an in-situ growth method, and grafting a silane coupling agent to obtain a modified carbon nano tube, namely the flame-retardant heat-conducting agent for the silicone rubber.
The invention also provides a preparation method of the flame-retardant heat-conducting agent for the silicone rubber, which comprises the following steps:
(a) ultrasonically dispersing a mixed solution of carbon nano tubes, nitric acid and sulfuric acid, reacting for 3-5 h at 40-60 ℃, filtering to obtain a reaction precipitate, washing to a pH value of 6.5-7.5, and drying to obtain a product, namely carboxylated carbon nano tube powder CNTs-COOH;
(b) slowly dropwise adding a soluble iron salt solution into the CNTs-COOH dispersion liquid, reacting for 8-12 h at 70-90 ℃, washing and drying a reacted precipitate to obtain CNTs-beta-FeOOH modified carbon nanotube powder with a three-dimensional structure;
(c) slowly adding a silane coupling agent into the ethanol solution of the CNTs-beta-FeOOH, reacting for 12-18 h at 70-90 ℃, washing and drying the reacted precipitate, and obtaining modified carbon nanotube powder, namely the flame-retardant heat-conducting agent for the silicone rubber.
Specifically, in the step (a), the drying is that the precipitate is dried in vacuum at 80 ℃ for 12 hours.
In the step (b), the concentration of the CNTs-COOH dispersion liquid is 0.1-0.4M; the concentration of the soluble ferric salt solution is 1-4M; the soluble ferric salt is ferric chloride hexahydrate. In the step (b) and the step (c), the washing and drying are to wash the precipitate with deionized water for three times, and then freeze-dry to obtain a powdery product; in the step (b) and the step (c), after the reaction is finished, standing for 2 hours, and then collecting the precipitate of the reaction. The silane coupling agent is KH-550.
In the step (c), the pH value of the ethanol solution of the CNTs-beta-FeOOH is adjusted to 3-5 by glacial acetic acid, ultrasonic dispersion is carried out for 1-2 h, and then a silane coupling agent is added.
When the flame-retardant heat-conducting agent is used for preparing a silicone rubber composite material, mixing the following components in parts by mass: 100 parts of silicon rubber, 30-50 parts of white carbon black, 1-3 parts of flame-retardant heat-conducting agent and 0.5-2 parts of dicumyl peroxide; the rubber vulcanization time is 15-25 min, and the vulcanization temperature is 165-175 ℃.
The flame-retardant heat-conducting agent prepared by the invention is mainly used for silicon rubber, mainly because the silicon rubber can form SiO in the combustion process 2 And then the flame-retardant heat-conducting agent migrates to the surface to form a white ceramic layer, but the ceramic layer has lower strength and cannot well protect a lower-layer matrix, and the flame-retardant heat-conducting agent prepared by the invention can well enhance the strength and compactness of the ceramic layer and isolate the transfer of heat and oxygen. And other rubbers can not generate a ceramic layer in the combustion process, and a compact and continuous insulating layer is difficult to form by simply depending on the reinforcing effect of the flame-retardant heat-conducting agent.
By adopting the scheme, after the prepared flame-retardant heat-conducting agent is added into the silicone rubber to prepare the composite material, the flame-retardant heat-conducting agent constructs a three-dimensional structure in the silicone rubber, and the carbon nano tube provides rapid phonon conduction and improves the heat-conducting property of the material. On the surface of the carbon nano tube, the radial distribution of the hydroxyl iron oxide nanocubes can effectively reduce the distance of a heat conduction path and reduce the energy loss in the heat conduction process; due to the lower thermal resistance, the conduction of phonons becomes simpler, and the heat conduction efficiency of the material is improved. Meanwhile, the modification of the iron oxyhydroxide on the carbon nano tube improves the flame retardant effect of the carbon nano tube, the surface modification of the silane coupling agent improves the dispersibility of the carbon nano tube in the silicon rubber, and the flame retardant property of the composite material is further improved.
Drawings
FIG. 1 is a heat release peak curve for the sample of example 1;
FIG. 2 is a graph of the total amount of heat released for the sample of example 1.
Detailed Description
The technical solution of the present invention is further described in detail by the following examples.
Example 1:
preparation of functionalized carbon nano-tube
a) 5g of CNTs were dissolved in 100ml of HNO 3 /H 2 SO 4 After being dispersed by ultrasound, the mixed solution is poured into a three-neck flask, and reacted at 40 ℃ for 4 hours, and the obtained acid-treated CNTs-COOH is diluted in water and filtered, washed to a neutral pH (pH 7.0), and vacuum-dried at 80 ℃ for 12 hours, to obtain CNTs-COOH powder.
b) 100ml of a 0.4M aqueous solution of carboxylated carbon nanotubes was prepared, sonicated for 1.5h, and transferred to a three-necked flask. Then, 10ml of a 3M aqueous solution of ferric chloride hexahydrate was slowly dropped thereinto, and after completion of the dropping, the reaction was carried out at 80 ℃ for 12 hours. And standing for 2 hours, collecting precipitates, washing with deionized water for three times, and freeze-drying to obtain the three-dimensional modified carbon nanotube powder (CNTs-beta-FeOOH).
c) Dissolving 3g of CNTs-beta-FeOOH powder in 100ml of ethanol solution, transferring the solution into a three-neck flask, slowly dropwise adding an acidic solution to adjust the pH value to 4, and performing ultrasonic dispersion. Then 5g KH550 and 15ml deionized water were slowly added dropwise thereto, and the reaction was carried out at 80 ℃ for 18 hours. And standing for 2 hours, collecting precipitates, washing with deionized water for three times, and freeze-drying to obtain modified carbon nanotube powder (KH550@ CNTs-beta-FeOOH).
Preparation and performance test of silicone rubber composite material
1. Sample preparation: the preparation of the flame retardant, thermally conductive silicone rubber is shown in table 1.
Table 1 example 1 formulation table (parts by mass)
And the blending ratio of the carbon nano tube, the iron oxyhydroxide and the silane coupling agent in the sample three is calculated according to the load ratio of the modified carbon nano tube.
Vulcanization conditions are as follows: vulcanization temperature: 170 ℃, vulcanization time: and 20 min.
2. Performance testing of the composite material: the micro calorimeter (MCC) test is carried out according to the ASTM-D7309-2007a standard, the weight of a sample is about 5mg, and the temperature rise rate is 1 ℃/s. Limiting Oxygen Index (LOI) testing was performed according to ASTM D2863-2012, standard test specimen size of 100X 10X 3mm 3 . The thermal conductivity test was carried out in accordance with ASTM D5470, Standard size of test specimens 50X 40X 5mm 3 The test was performed at room temperature. The mechanical property test is carried out according to the GB/T6344-2008 standard, and the tensile rate of the sample is 500 mm/min. Fig. 1 is a graph of the peak heat release (phr) and Total Heat Release (THR) for sample one, sample two, and sample three. Table 2 shows the peak heat release (phr), Total Heat Release (THR), Limiting Oxygen Index (LOI), thermal conductivity, and tensile strength, elongation at break of sample one, sample two, and sample three. Therefore, the flame-retardant and heat-conducting rubber prepared by the invention has excellent flame-retardant property, heat conduction property and mechanical property.
Table 2 performance test data for example 1 silicone rubber composites
The data in the table show that after the modified carbon nano tube prepared by the scheme of the invention is added, the heat release peak value (PHRR) and the total heat release amount (THR) of the silicone rubber are greatly reduced, the thermal conductivity, the tensile strength and the elongation at break are also greatly improved, and compared with the blending of the carbon nano tube, the iron oxyhydroxide and the silane coupling agent, the effect is still obvious, so that the flame-retardant heat-conducting agent prepared by the scheme of the invention can improve the flame retardance, the heat conductivity and the mechanical property of the silicone rubber.
Example 2
Preparation of functionalized carbon nano-tube
a) 5g of CNTs were dissolved in 100ml of HNO 3 /H 2 SO 4 After being dispersed by ultrasound, the mixed solution is poured into a three-neck flask, and reacted at 50 ℃ for 4 hours, and the obtained acid-treated CNTs-COOH is diluted in water and filtered, washed to a neutral pH (pH 7.0), and vacuum-dried at 80 ℃ for 12 hours, to obtain CNTs-COOH powder.
b) 100ml of a 0.2M aqueous solution of carboxylated carbon nanotubes was prepared, sonicated for 1.5h, and transferred to a three-necked flask. Then, 10ml of a 2M aqueous solution of ferric chloride hexahydrate was slowly dropped thereinto, and after completion of the dropping, the reaction was carried out at 80 ℃ for 8 hours. And standing for 2 hours, collecting precipitates, washing with deionized water for three times, and freeze-drying to obtain the three-dimensional modified carbon nanotube powder (CNTs-beta-FeOOH).
c) Dissolving 4g of CNTs-beta-FeOOH powder in 100ml of ethanol solution, transferring the solution into a three-neck flask, slowly dropwise adding an acidic solution to adjust the pH value to 3-5, and performing ultrasonic dispersion. Then 3-4g KH550 and 10ml deionized water are slowly dropped into the mixture, and the mixture is reacted for 12 hours at 80 ℃. And standing for 2 hours, collecting precipitates, washing with deionized water for three times, and freeze-drying to obtain modified carbon nanotube powder (KH550@ CNTs-beta-FeOOH).
Preparation and performance test of silicone rubber composite material
1. Sample preparation: the preparation of the flame retardant, thermally conductive silicone rubber is shown in table 3.
Table 3 example 2 sample formulation table (parts by mass)
Vulcanization conditions are as follows: vulcanization temperature: 175 ℃, vulcanization time: and 15 min.
2. Performance testing of the composite material: the micro calorimeter (MCC) test is carried out according to the ASTM-D7309-2007a standard, the weight of a sample is about 5mg, and the temperature rising rate is 1 ℃/s. Limiting Oxygen Index (LOI)The test was carried out according to ASTM D2863-2012, standard dimensions of test specimens of 100X 10X 3mm 3 . The thermal conductivity test was carried out in accordance with ASTM D5470, Standard size of test specimens 50X 40X 5mm 3 The test was performed at room temperature. Table 4 shows the heat release peak (phr), Total Heat Release (THR), Limiting Oxygen Index (LOI), and thermal conductivity for sample four and sample five. Therefore, the flame-retardant and heat-conducting silicon rubber prepared by the invention has excellent flame-retardant performance and heat conduction.
Table 4 performance test data for silicone rubber composites of example 2
Example 3
Preparation of functionalized carbon nano-tube
a) 5g of CNTs were dissolved in 100ml of HNO 3 /H 2 SO 4 After being dispersed by ultrasound, the mixed solution is poured into a three-neck flask, reacted for 4 hours at 60 ℃, and the obtained acid-treated CNTs-COOH is diluted in water and filtered, washed to a neutral pH (pH 7.0), and vacuum-dried for 12 hours at 80 ℃ to obtain CNTs-COOH powder.
b) 100ml of a 0.4M aqueous solution of carboxylated carbon nanotubes was prepared, sonicated for 1.5h, and transferred to a three-necked flask. Then, 10ml of a 3M aqueous solution of ferric chloride hexahydrate was slowly dropped thereinto, and after completion of the dropping, the reaction was carried out at 80 ℃ for 12 hours. And standing for 2 hours, collecting precipitates, washing with deionized water for three times, and freeze-drying to obtain the three-dimensional modified carbon nanotube powder (CNTs-beta-FeOOH).
c) Dissolving 5g of CNTs-beta-FeOOH powder in 100ml of ethanol solution, transferring the solution into a three-neck flask, slowly dropwise adding an acidic solution to adjust the pH value to 3-5, and performing ultrasonic dispersion. Then 3-3g KH550 and 5ml deionized water are slowly dropped into the mixture, and the mixture is reacted for 15 hours at 80 ℃. And standing for 2 hours, collecting precipitates, washing with deionized water for three times, and freeze-drying to obtain modified carbon nanotube powder (KH550@ CNTs-beta-FeOOH).
Preparation and performance test of silicone rubber composite material
1. Sample preparation: the preparation of the flame retardant, thermally conductive silicone rubber is shown in table 5.
Table 5 example 3 sample formulation table (parts by mass)
Vulcanization conditions are as follows: vulcanization temperature: 165 ℃, vulcanization time: and (5) 25 min.
2. Performance testing of the composite material: the micro calorimeter (MCC) test is carried out according to the ASTM-D7309-2007a standard, the weight of a sample is about 5mg, and the temperature rise rate is 1 ℃/s. Limiting Oxygen Index (LOI) testing was performed according to ASTM D2863-2012, standard test specimen size of 100X 10X 3mm 3 . The thermal conductivity test was carried out in accordance with ASTM D5470, Standard size of test specimens 50X 40X 5mm 3 The test was performed at room temperature. Table 6 shows the heat release peak (pHRR), Total Heat Release (THR), Limiting Oxygen Index (LOI), and thermal conductivity of sample six and sample seven. Therefore, the flame-retardant heat-conducting rubber prepared by the invention has excellent flame-retardant performance and heat conduction.
Table 6 performance test data for example 3 silicone rubber composites
Claims (10)
1. A flame-retardant heat-conducting agent for silicone rubber is characterized in that: generating iron oxyhydroxide on the surface of the carbon nano tube by an in-situ growth method, and grafting a silane coupling agent to obtain a modified carbon nano tube, namely the flame-retardant heat-conducting agent for the silicone rubber.
2. A method for preparing a flame retardant and heat conductive agent for silicone rubber as defined in claim 1, comprising the steps of:
(a) ultrasonically dispersing a mixed solution of carbon nano tubes, nitric acid and sulfuric acid, reacting for 3-5 h at 40-60 ℃, filtering to obtain a reaction precipitate, washing to a pH value of 6.5-7.5, and drying to obtain a product, namely carboxylated carbon nano tube powder CNTs-COOH;
(b) slowly dropwise adding a soluble iron salt solution into the CNTs-COOH dispersion liquid, reacting for 8-12 h at 70-90 ℃, washing and drying a reacted precipitate to obtain CNTs-beta-FeOOH modified carbon nanotube powder with a three-dimensional structure;
(c) slowly adding a silane coupling agent into an ethanol solution of CNTs-beta-FeOOH, reacting for 12-18 h at 70-90 ℃, washing and drying a reaction precipitate, and obtaining modified carbon nano tube powder, namely the flame-retardant heat-conducting agent for the silicone rubber.
3. The method for preparing a flame retardant and heat conductive agent for silicone rubber according to claim 2, characterized in that: in the step (a), the drying is that the precipitate is dried in vacuum at 80 ℃ for 12 hours.
4. The method for preparing a flame retardant and heat conductive agent for silicone rubber according to claim 2, characterized in that: in the step (b), the concentration of the CNTs-COOH dispersion liquid is 0.1-0.4M; the concentration of the soluble ferric salt solution is 1-4M.
5. The method for producing a flame-retardant and heat-conductive agent for silicone rubber according to claim 2, characterized in that: the soluble ferric salt in step (b) is ferric chloride hexahydrate.
6. The method for preparing a flame-retardant and thermally conductive agent for silicone rubber according to claim 2, characterized in that: in the step (b) and the step (c), the washing and drying are to wash the precipitate with deionized water three times, and then freeze-dry to obtain a powdery product.
7. The method for preparing a flame retardant and heat conductive agent for silicone rubber according to claim 2, characterized in that: in the step (b) and the step (c), after the reaction is finished, standing for 2 hours, and then collecting the precipitate of the reaction.
8. The flame-retardant and thermally conductive agent for silicone rubber according to claim 1 or the method for producing a flame-retardant and thermally conductive agent for silicone rubber according to claim 2, characterized in that: the silane coupling agent is KH-550.
9. The method for preparing a flame-retardant and thermally conductive agent for silicone rubber according to claim 2, characterized in that: in the step (c), the pH value of the ethanol solution of the CNTs-beta-FeOOH is adjusted to 3-5 by glacial acetic acid, ultrasonic dispersion is carried out for 1-2 h, and then a silane coupling agent is added.
10. The method for producing the flame-retardant and thermally conductive agent for silicone rubber according to claim 1 or the flame-retardant and thermally conductive agent for silicone rubber according to any one of claims 2 to 9, characterized in that: when the flame-retardant heat-conducting agent is used for preparing a silicone rubber composite material, mixing the following components in parts by mass: 100 parts of silicon rubber, 30-50 parts of white carbon black, 1-3 parts of flame-retardant heat-conducting agent and 0.5-2 parts of dicumyl peroxide; the rubber vulcanization time is 15-25 min, and the vulcanization temperature is 165-175 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210656420.XA CN115124764A (en) | 2022-06-10 | 2022-06-10 | Flame-retardant heat-conducting agent for silicone rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210656420.XA CN115124764A (en) | 2022-06-10 | 2022-06-10 | Flame-retardant heat-conducting agent for silicone rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115124764A true CN115124764A (en) | 2022-09-30 |
Family
ID=83377675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210656420.XA Pending CN115124764A (en) | 2022-06-10 | 2022-06-10 | Flame-retardant heat-conducting agent for silicone rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115124764A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302970A (en) * | 1999-04-19 | 2000-10-31 | Suzuki Sogyo Co Ltd | Thermally conductive silicone rubber composition, its molding product and it applied product |
| CN103709761A (en) * | 2013-12-02 | 2014-04-09 | 天津大学 | Iron oxide modified carbon nanotube-silicone rubber composite material and preparation method thereof |
| CN108485268A (en) * | 2018-02-28 | 2018-09-04 | 天长市荣盛有机硅科技有限公司 | A kind of silicon rubber Heat Conduction Material and preparation method thereof containing carbon nanotube |
| CN110947407A (en) * | 2019-11-20 | 2020-04-03 | 东莞理工学院 | Iron nitride carbon nanotube composite material and preparation method and application thereof |
| CN112064339A (en) * | 2020-08-28 | 2020-12-11 | 山东非金属材料研究所 | Iron oxyhydroxide-copper-clad carbon nanotube coaxial core-shell material and preparation method and application thereof |
-
2022
- 2022-06-10 CN CN202210656420.XA patent/CN115124764A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302970A (en) * | 1999-04-19 | 2000-10-31 | Suzuki Sogyo Co Ltd | Thermally conductive silicone rubber composition, its molding product and it applied product |
| CN103709761A (en) * | 2013-12-02 | 2014-04-09 | 天津大学 | Iron oxide modified carbon nanotube-silicone rubber composite material and preparation method thereof |
| CN108485268A (en) * | 2018-02-28 | 2018-09-04 | 天长市荣盛有机硅科技有限公司 | A kind of silicon rubber Heat Conduction Material and preparation method thereof containing carbon nanotube |
| CN110947407A (en) * | 2019-11-20 | 2020-04-03 | 东莞理工学院 | Iron nitride carbon nanotube composite material and preparation method and application thereof |
| CN112064339A (en) * | 2020-08-28 | 2020-12-11 | 山东非金属材料研究所 | Iron oxyhydroxide-copper-clad carbon nanotube coaxial core-shell material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Processing, thermal conductivity and flame retardant properties of silicone rubber filled with different geometries of thermally conductive fillers: A comparative study | |
| Pan et al. | Highly thermally conductive 3D BN/MWCNTs/C spatial network composites with improved electrically insulating and flame retardancy prepared by biological template assisted method | |
| Hu et al. | Enhanced thermal conductivity by constructing 3D-networks in poly (vinylidene fluoride) composites via positively charged hexagonal boron nitride and silica coated carbon nanotubes | |
| Qu et al. | Improved flame retardancy of epoxy resin composites modified with a low additive content of silica-microencapsulated phosphazene flame retardant | |
| CN101955631B (en) | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material | |
| Chen et al. | Synergistic effect of carbon nanotubes bonded graphene oxide to enhance the flame retardant performance of waterborne intumescent epoxy coatings | |
| CN113462127A (en) | Modified boron nitride, composite material containing modified boron nitride, preparation method and application of modified boron nitride | |
| CN108976588B (en) | Flame-retardant antistatic EVA foam composite material and preparation method thereof | |
| Gong et al. | Construction of interface-engineered two-dimensional nanohybrids towards superb fire resistance of epoxy composites | |
| Chen et al. | Performance of silicone rubber composites using boron nitride to replace alumina tri‐hydrate | |
| Fan et al. | Thermal conductivity and mechanical properties of high density polyethylene composites filled with silicon carbide whiskers modified by cross-linked poly (vinyl alcohol) | |
| Wang et al. | Study the mechanism that carbon nanotubes improve thermal stability of polymer composites: An ingenious design idea with coating silica on CNTs and valuable in engineering applications | |
| Yang et al. | Enhancing through-plane thermal conductivity of epoxy-based composites via surface treatment of boron nitride cured with a flame retardant phosphazene-based curing agent | |
| Chen et al. | A copper organic phosphonate functionalizing boron nitride nanosheet for PVA film with excellent flame retardancy and improved thermal conductive property | |
| CN114605833A (en) | Flame-retardant heat-conducting silicone rubber material and preparation method thereof | |
| Liu et al. | Constructing a novel synergistic flame retardant by hybridization of zeolitic imidazolate framework‐67 and graphene oxide for thermoplastic polyurethane | |
| Zhang et al. | High-transparency polysilsesquioxane/glycidyl-azide-polymer resin and its fiberglass-reinforced composites with excellent fire resistance, mechanical properties, and water resistance | |
| Zhuang et al. | Enhanced thermal conductivity and mechanical properties of natural rubber-based composites co-incorporated with surface treated alumina and reduced graphene oxide | |
| CN109608697A (en) | A kind of modified MoS of phosphorus-containing compound2The preparation method and applications of nanoscale twins | |
| CN107778865A (en) | A kind of CNT composite heat conducting material and preparation method thereof | |
| CN112250917A (en) | Preparation method of high-thermal-conductivity natural rubber composite material | |
| Chen et al. | Multi-walled carbon nanotubes encapsulated by graphitic carbon nitride with simultaneously co-doping of B and P and ammonium polyphosphate to improve flame retardancy of unsaturated polyester resins | |
| Chai et al. | An eco-friendly, bio-inspired and synergistic flame retardant system with outstanding water tolerance and ultra-low addition for silicone rubber | |
| CN115028892A (en) | Three-dimensional structure modified boron nitride and preparation method and application thereof | |
| CN115124764A (en) | Flame-retardant heat-conducting agent for silicone rubber 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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220930 |
|
| RJ01 | Rejection of invention patent application after publication |