CN114989617A - Preparation method of ceramic silicon rubber material with high weather resistance - Google Patents
Preparation method of ceramic silicon rubber material with high weather resistance Download PDFInfo
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- CN114989617A CN114989617A CN202210634761.7A CN202210634761A CN114989617A CN 114989617 A CN114989617 A CN 114989617A CN 202210634761 A CN202210634761 A CN 202210634761A CN 114989617 A CN114989617 A CN 114989617A
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- silicone rubber
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- weather resistance
- flame retardant
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 111
- 239000000919 ceramic Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004945 silicone rubber Substances 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract 14
- 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 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000003063 flame retardant Substances 0.000 claims description 32
- -1 alkyl phosphoric acid modified silicon dioxide Chemical class 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 238000004073 vulcanization Methods 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 18
- 239000005060 rubber Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 16
- 239000012796 inorganic flame retardant Substances 0.000 claims description 16
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 16
- 239000000347 magnesium hydroxide Substances 0.000 claims description 16
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 150000004706 metal oxides Chemical class 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 125000003703 phosphorus containing inorganic group Chemical group 0.000 claims description 16
- 150000003058 platinum compounds Chemical class 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 239000010452 phosphate Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 229920002545 silicone oil Polymers 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000010456 wollastonite Substances 0.000 claims description 8
- 229910052882 wollastonite Inorganic materials 0.000 claims description 8
- MVQUCQUAYDBXMV-UHFFFAOYSA-N 12-sulfanyldodecyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCCCCCCCCCCS MVQUCQUAYDBXMV-UHFFFAOYSA-N 0.000 claims description 7
- PDDYFPPQDKRJTK-UHFFFAOYSA-N diphenyl(prop-2-enyl)phosphane Chemical compound C=1C=CC=CC=1P(CC=C)C1=CC=CC=C1 PDDYFPPQDKRJTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- POPVULPQMGGUMJ-UHFFFAOYSA-N octasilsesquioxane cage Chemical compound O1[SiH](O[SiH](O2)O[SiH](O3)O4)O[SiH]4O[SiH]4O[SiH]1O[SiH]2O[SiH]3O4 POPVULPQMGGUMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 230000032683 aging Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of silicon rubber materials, in particular to a preparation method of a ceramic silicon rubber material with strong weather resistance. The ceramic silicone rubber tube prepared by the method can obviously improve the weather resistance of the existing ceramic silicone rubber tube, so that the service life of the ceramic silicone rubber tube in a new energy battery pack is obviously prolonged.
Description
Technical Field
The invention relates to the field of silicon rubber materials, in particular to a preparation method of a ceramic silicon rubber material with strong weather resistance.
Background
Silicone rubber refers to rubber having a backbone composed of alternating silicon and oxygen atoms, with the silicon atoms typically having two organic groups attached to them. Conventional silicone rubbers consist predominantly of siloxane segments containing methyl groups and small amounts of vinyl groups. The introduction of phenyl can improve the high and low temperature resistance of the silicone rubber, and the introduction of trifluoropropyl and cyano can improve the temperature resistance and oil resistance of the silicone rubber. The silicon rubber has good low temperature resistance, and can still work at the temperature of minus 55 ℃. After the introduction of phenyl, a temperature of-73 ℃ can be reached. The silicon rubber has outstanding heat resistance, can work for a long time at 180 ℃, can still have elasticity for a plurality of weeks or more even at the temperature slightly higher than 200 ℃, and can instantaneously resist the high temperature of more than 300 ℃.
In recent years, the novel fireproof composite material, namely ceramic silicon rubber, is prepared by taking silicon rubber as a matrix, adding inorganic fillers such as a ceramic forming filler, a fluxing agent, a reinforcing agent and the like, and vulcanizing the matrix, and the novel fireproof composite material has various excellent performances of the silicon rubber matrix at normal temperature, such as good insulating property, aging resistance, electric arc resistance, ablation resistance, high and low temperature resistance and the like, and when high temperature or flame is encountered, a ceramic layer with certain hardness and strength is formed on the surface of the material, so that flame combustion is further prevented, and valuable time is won for people to evacuate in case of fire. Of course, due to the introduction of the inorganic filler, the ceramic silicone rubber generally has the defect that the mechanical properties such as hardness, tensile strength and the like of the ceramic silicone rubber are rapidly reduced under the conditions of high temperature, high humidity and high temperature aging, and the defect is the key for influencing the long-term use of the ceramic silicone rubber tube which is applied to a new energy automobile battery pack and plays a role in protecting a water tube.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a ceramic silicon rubber material with strong weather resistance, which comprises the following raw materials in parts by weight:
100-120 parts of methyl vinyl silicone rubber, 20-40 parts of alkyl phosphoric acid modified silicon dioxide, 5-20 parts of metal oxide powder, 5-8 parts of fluxing agent, 20-30 parts of flame retardant, 2-12 parts of hydroxyl silicone oil, 30-60 parts of wollastonite, 0.001-0.1 part of platinum compound and 1-5 parts of DBPMH.
Furthermore, the mol content of vinyl in the methyl vinyl silicone rubber is 0.08-0.12%.
Further, the preparation method of the silica modified by the alkyl phosphate comprises the following operation steps:
according to the weight portion, 100-200 portions of silicon dioxide with the granularity of 5-15 mu m and 5-10 portions of octavinyl octasilsesquioxane are added into a high-speed mixer and heated to 80-100 ℃ for reaction for 0.2-0.8 h; then adding 1-4 parts of tetramethylammonium hydroxide, 3-6 parts of 12-mercapto dodecyl phosphoric acid, 3-6 parts of allyl diphenyl phosphine and 20-30 parts of solvent oil, heating to 80-100 ℃, mixing at high speed for 0.2-1.2h, and drying to obtain the silica modified by alkyl phosphoric acid.
Further, the metal oxide is selected from one or more of aluminum oxide nanoparticles, ferric oxide nanoparticles and zirconium dioxide nanoparticles.
Further, the fluxing agent is selected from glass powder and/or zinc oxide.
Further, the flame retardant comprises a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant and a phosphorus-containing organic flame retardant.
Further, the mass ratio of the aluminum hydroxide, the magnesium hydroxide, the phosphorus-containing inorganic flame retardant and the phosphorus-containing organic flame retardant is 1 (0.5-1): (0.3-1): 0.1-0.5).
Further, the platinum compound is chloroplatinic acid or a tetramethyldivinylsiloxane-platinum complex.
In addition, the invention also provides a preparation method of the ceramic silicone rubber tube with strong weather resistance, which comprises the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
Furthermore, the vulcanization temperature is 160-180 ℃, the vulcanization pressure is 2-5MPa, and the vulcanization time is 2-7 min.
The ceramic silicone rubber tube with high weather resistance has a tensile strength change rate of 3-7% and a hardness change amplitude of 3-6Shore A.
According to the preparation method of the ceramic silicon rubber material with strong weather resistance, the alkyl phosphate modified silicon dioxide is prepared by using 12-mercapto dodecyl phosphoric acid and allyl diphenyl phosphine modified silicon dioxide, and is used as an important filling material in a ceramic silicon rubber raw material, so that the mechanical properties of a ceramic silicon rubber pipe in a high-temperature, high-humidity and continuous high-temperature environment can be greatly reserved; on the other hand, the mechanical property of the prepared ceramic silicone rubber tube under high-low temperature alternating conditions can be improved, the weather resistance of the material is obviously improved, and the ceramic silicone rubber tube can stably protect a water pipe in a new energy battery pack for a long time.
Detailed Description
The invention is further illustrated by the following specific examples:
example 1
A preparation method of a ceramic silicon rubber material with strong weather resistance comprises the following raw materials in parts by weight:
100kg of methyl vinyl silicone rubber, 20kg of alkyl phosphate modified silicon dioxide, 5kg of metal oxide powder, 5kg of fluxing agent, 20kg of flame retardant, 3kg of hydroxyl silicone oil and 30kg of wollastonite, wherein the platinum compound is 0.01kg of platinum and DBPMH1.7kg of platinum.
The molar content of vinyl in the methyl vinyl silicone rubber is 0.08%.
The preparation method of the alkyl phosphate modified silicon dioxide comprises the following operation steps:
100kg of silicon dioxide with the average particle size of 10 mu m and 5kg of octavinyl octasilsesquioxane are added into a high-speed mixer and heated to 80 ℃ for reaction for 0.8 h; then 1kg of tetramethylammonium hydroxide, 3kg of 12-mercaptododecylphosphoric acid, 3kg of allyldiphenylphosphine were added; 20kg of solvent oil, keeping the temperature at 80 ℃, mixing for 0.2h at high speed, and drying to obtain the silica modified by the alkyl phosphate.
The metal oxide is alumina nanoparticles.
The fluxing agent is glass powder.
The flame retardant is a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant and a phosphorus-containing organic flame retardant.
The mass ratio of the aluminum hydroxide to the magnesium hydroxide to the phosphorus-containing inorganic flame retardant to the phosphorus-containing organic flame retardant is 1:0.5:0.3: 0.1.
The platinum compound is chloroplatinic acid.
A preparation method of a ceramic silicone rubber tube with strong weather resistance comprises the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
Further, the vulcanization temperature is 160 ℃, the vulcanization pressure is 2MPa, and the vulcanization time is 7 min.
Further, the prepared ceramic silicon rubber tube has the inner diameter of 25.2mm, the outer diameter of 28.1mm and the density of 1.59g/cm 3 。
Example 2
A preparation method of a ceramic silicon rubber material with strong weather resistance comprises the following raw materials in parts by weight:
110kg of methyl vinyl silicone rubber, 31kg of alkyl phosphoric acid modified silicon dioxide, 13kg of metal oxide powder, 7kg of fluxing agent, 25kg of flame retardant, 8kg of hydroxyl silicone oil and 50kg of wollastonite, wherein the platinum compound is 0.01kg of platinum and DBPMH3.5kg of platinum.
The molar content of vinyl in the methyl vinyl silicone rubber is 0.10%.
The preparation method of the alkyl phosphate modified silicon dioxide comprises the following operation steps:
adding 150kg of silicon dioxide with the particle size of 10 mu m and 8kg of octavinyl octasilsesquioxane into a high-speed mixer, and heating to 90 ℃ to react for 0.5 h; then 2kg of tetramethylammonium hydroxide, 4kg of 12-mercaptododecylphosphoric acid, 4kg of allyldiphenylphosphine were added; heating 25kg solvent oil to 90 ℃, mixing for 0.6h at high speed, and drying to obtain the silica modified by the alkyl phosphoric acid.
The metal oxide is zirconium dioxide nano-particles.
The fluxing agent is zinc oxide.
The flame retardant is a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant and a phosphorus-containing organic flame retardant.
The mass ratio of the aluminum hydroxide to the magnesium hydroxide to the phosphorus-containing inorganic flame retardant to the phosphorus-containing organic flame retardant is 1:0.8:0.6: 0.3.
The platinum compound is a tetramethyldivinylsiloxane-platinum complex.
A preparation method of a ceramic silicone rubber tube with strong weather resistance comprises the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
Further, the vulcanization temperature is 170 ℃, the vulcanization pressure is 3MPa, and the vulcanization time is 5 min.
Further, the prepared ceramic silicon rubber tube has the inner diameter of 16.1mm, the outer diameter of 19.2mm and the density of 1.61g/cm 3 。
Example 3
A preparation method of a ceramic silicon rubber material with strong weather resistance comprises the following raw materials in parts by weight:
120kg of methyl vinyl silicone rubber, 40kg of alkyl phosphoric acid modified silicon dioxide, 20kg of metal oxide powder, 8kg of fluxing agent, 30kg of flame retardant, 12kg of hydroxyl silicone oil, 60kg of wollastonite, 0.1kg of platinum compound according to the parts of platinum and DBPMH5 kg.
The molar content of vinyl in the methyl vinyl silicone rubber is 0.12 percent.
The preparation method of the alkyl phosphate modified silicon dioxide comprises the following operation steps:
200kg of silicon dioxide with the average particle size of 15 mu m and 10kg of octavinyl octasilsesquioxane are added into a high-speed mixer and heated to 100 ℃ for reaction for 0.2 h; 4kg of tetramethylammonium hydroxide, 6kg of 12-mercaptododecylphosphoric acid and 6kg of allyldiphenylphosphine were subsequently added; 30kg of solvent oil, heating to 100 ℃, mixing for 1.2h at high speed, and drying to obtain the silica modified by the alkyl phosphate.
The metal oxide is ferric oxide nano particles.
The fluxing agent is selected from glass powder and zinc oxide, and the mass ratio is 1: 1.
The flame retardant comprises a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant, and a phosphorus-containing organic flame retardant.
The mass ratio of the aluminum hydroxide to the magnesium hydroxide to the phosphorus-containing inorganic flame retardant to the phosphorus-containing organic flame retardant is 1:1:1: 0.5.
The platinum compound is a tetramethyldivinylsiloxane-platinum complex.
A preparation method of a ceramic silicone rubber tube with strong weather resistance comprises the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
Further, the vulcanization temperature is 180 ℃, the vulcanization pressure is 5MPa, and the vulcanization time is 2 min.
Further, the prepared ceramic silicon rubber tube has the inner diameter of 21.9mm, the outer diameter of 25.1mm and the density of 1.6g/cm 3 。
Comparative example 1
A preparation method of a ceramic silicon rubber material with strong weather resistance comprises the following raw materials in parts by weight:
100kg of methyl vinyl silicone rubber, 20kg of alkyl phosphate modified silicon dioxide, 5kg of metal oxide powder, 5kg of fluxing agent, 20kg of flame retardant, 3kg of hydroxyl silicone oil and 30kg of wollastonite, wherein the platinum compound is 0.01kg of platinum and DBPMH1.7kg of platinum.
The vinyl molar content in the methyl vinyl silicone rubber is 0.08%.
The preparation method of the alkyl phosphate modified silicon dioxide comprises the following operation steps:
adding 100kg of silicon dioxide with the average particle size of 10 mu m into a high-speed mixer, and heating to 80 ℃; 1kg of tetramethylammonium hydroxide, 3kg of 12-mercaptododecylphosphoric acid and 3kg of allyldiphenylphosphine were subsequently added; 20kg of solvent oil, keeping the temperature at 80 ℃, mixing for 0.2h at high speed, and drying to obtain the silica modified by the alkyl phosphate.
The metal oxide is alumina nanoparticles.
The fluxing agent is glass powder.
The flame retardant is a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant and a phosphorus-containing organic flame retardant.
The mass ratio of the aluminum hydroxide to the magnesium hydroxide to the phosphorus-containing inorganic flame retardant to the phosphorus-containing organic flame retardant is 1:0.5:0.3: 0.1.
The platinum compound is chloroplatinic acid.
A preparation method of a ceramic silicone rubber tube with strong weather resistance comprises the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
Further, the vulcanization temperature is 160 ℃, the vulcanization pressure is 2MPa, and the vulcanization time is 7 min.
Further, the prepared ceramic silicon rubber tube has the inner diameter of 25.1mm, the outer diameter of 28.1mm and the density of 1.54g/cm 3 。
Comparative example 2
A preparation method of a ceramic silicon rubber material with strong weather resistance comprises the following raw materials in parts by weight:
100kg of methyl vinyl silicone rubber, 20kg of alkyl phosphate modified silicon dioxide, 5kg of metal oxide powder, 5kg of fluxing agent, 20kg of flame retardant, 3kg of hydroxyl silicone oil and 30kg of wollastonite, wherein the platinum compound is 0.01kg of platinum and DBPMH1.7kg of platinum.
The molar content of vinyl in the methyl vinyl silicone rubber is 0.08%.
The preparation method of the alkyl phosphate modified silicon dioxide comprises the following operation steps:
100kg of silicon dioxide with the average particle size of 10 mu m and 5kg of octavinyl octasilsesquioxane are added into a high-speed mixer and heated to 80 ℃ for reaction for 0.8 h; 1kg of tetramethylammonium hydroxide, 3kg of allyldiphenylphosphine were then added; 20kg of solvent oil, keeping the temperature at 8 ℃ and mixing for 0.2h at high speed, and drying to obtain the alkyl modified silicon dioxide.
The metal oxide is alumina nanoparticles.
The fluxing agent is glass powder.
The flame retardant is a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant and a phosphorus-containing organic flame retardant.
The mass ratio of the aluminum hydroxide to the magnesium hydroxide to the phosphorus-containing inorganic flame retardant to the phosphorus-containing organic flame retardant is 1:0.5:0.3: 0.1.
The platinum compound is chloroplatinic acid.
A preparation method of a ceramic silicone rubber tube with strong weather resistance comprises the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
Further, the vulcanization temperature is 160 ℃, the vulcanization pressure is 2MPa, and the vulcanization time is 7 min.
Further, the prepared ceramic silicon rubber tube has the inner diameter of 24.9mm, the outer diameter of 28mm and the density of 1.58g/cm 3 。
Comparative example 3
A preparation method of a ceramic silicon rubber material with strong weather resistance comprises the following components:
100kg of methyl vinyl silicone rubber, 20kg of common silicon dioxide, 5kg of metal oxide powder, 5kg of fluxing agent, 20kg of flame retardant, 3kg of hydroxyl silicone oil and 30kg of wollastonite, wherein the platinum compound is 0.01kg in parts of platinum and 1.7kg of DBPMH.
The molar content of vinyl in the methyl vinyl silicone rubber is 0.08%.
The metal oxide is alumina nanoparticles.
The fluxing agent is glass powder.
The flame retardant is a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant and a phosphorus-containing organic flame retardant.
The mass ratio of the aluminum hydroxide to the magnesium hydroxide to the phosphorus-containing inorganic flame retardant to the phosphorus-containing organic flame retardant is 1:0.5:0.3: 0.1.
The platinum compound is chloroplatinic acid.
A preparation method of a ceramic silicone rubber tube with strong weather resistance comprises the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
Further, the vulcanization temperature is 160 ℃, the vulcanization pressure is 2MPa, and the vulcanization time is 7 min.
Further, the prepared ceramic silicon rubber tube has the inner diameter of 25mm, the outer diameter of 28.2mm and the density of 1.64g/cm 3 . The test method comprises the following steps:
and (3) testing hardness: GB/T531.1-2008 hardness of plastic and rubber indentation hardness (Shore hardness) was measured using a durometer
Tensile strength: determination of tensile stress strain performance of GB/T528-2009 vulcanized rubber or thermoplastic rubber
Weather resistance test conditions:
1. high-temperature high-humidity aging detection conditions:
the ceramic silicone rubber tube is placed in an experimental box for 1000 hours at the temperature of 85 ℃ and the humidity of 85 percent, and comparison data of the hardness and the tensile strength of the ceramic silicone rubber tube before and after the ceramic silicone rubber tube is placed are recorded.
2. High-temperature aging detection conditions:
placing the ceramic silicone rubber tube in an experimental box for 1000h at the temperature of 150 ℃; recording comparison data of the hardness and the tensile strength of the ceramic silicone rubber tube before and after placement;
placing the ceramic silicone rubber tube in an experimental box for 1000 hours at 180 ℃; and recording comparison data of the hardness and the tensile strength of the ceramic silicone rubber tube before and after the ceramic silicone rubber tube is placed.
3. High and low temperature alternation test conditions:
the ceramic silicon rubber tube is placed in an experimental box, and the alternating circulation is completed for 500 times in a gradient manner at the temperature of not more than 5 ℃/min between-40 ℃ and 85 ℃. And in each cycle, respectively keeping for 15min at the highest temperature and the lowest temperature, and recording comparison data of the hardness and the tensile strength of the ceramic silicon rubber tube before and after the ceramic silicon rubber tube is placed.
Since the tensile strength test of the ceramic silicone rubber tube is a destructive test, the ceramic silicone rubber tubes with the same thickness and length prepared in the same batch are selected for test comparison.
The following are the results of the comparison of the hardness and tensile strength of the ceramic silicone rubber tubes prepared in examples 1 to 3 and comparative examples 1 to 3 before and after the weather resistance test.
TABLE 1 weather resistance testing table for ceramic silicone rubber tube
From the analysis of the above table, the ceramic silicone rubber tube has small mechanical property change amplitude and good tensile property in high-temperature, high-humidity and high-temperature environments, and the silicon dioxide is subjected to alkyl phosphoric acid modification and used as an important filling material in the ceramic silicone rubber raw material, so that the mechanical properties of the ceramic silicone rubber tube in high-temperature, high-humidity and high-temperature environments are greatly maintained, meanwhile, the mechanical properties of the ceramic silicone rubber tube in high-temperature, high-humidity and high-temperature alternating environments are also improved, the weather resistance of the ceramic silicone rubber tube is remarkably improved, and the service life of the ceramic silicone rubber tube in a new energy battery pack is remarkably prolonged.
Claims (10)
1. A preparation method of a ceramic silicon rubber material with strong weather resistance comprises the following raw materials in parts by weight:
100-120 parts of methyl vinyl silicone rubber, 20-40 parts of alkyl phosphoric acid modified silicon dioxide, 5-20 parts of metal oxide powder, 5-8 parts of fluxing agent, 20-30 parts of flame retardant, 2-12 parts of hydroxyl silicone oil, 30-60 parts of wollastonite, 0.001-0.1 part of platinum compound and 1-5 parts of DBPMH.
2. The method for preparing the ceramic silicone rubber material with strong weather resistance according to claim 1, wherein the method comprises the following steps: the molar content of vinyl in the methyl vinyl silicone rubber is 0.08-0.12%.
3. The method for preparing the ceramic silicone rubber material with strong weather resistance according to claim 1, wherein the method comprises the following steps: the preparation method of the alkyl phosphate modified silicon dioxide comprises the following operation steps:
according to the weight portion, 100-200 portions of silicon dioxide with the particle size of 5-15 μm and 5-10 portions of octavinyl octasilsesquioxane are added into a high-speed mixer and heated to 80-100 ℃ for reaction for 0.2-0.8 h; then adding 1-4 parts of tetramethylammonium hydroxide, 3-6 parts of 12-mercapto dodecyl phosphoric acid, 3-6 parts of allyl diphenyl phosphine and 20-30 parts of solvent oil, heating to 80-100 ℃, mixing at high speed for 0.2-1.2h, and drying to obtain the silica modified by alkyl phosphoric acid.
4. The method for preparing high weather-resistant ceramic silicone rubber material according to claim 1, wherein: the metal oxide is selected from one or more of aluminum oxide nanoparticles, ferric oxide nanoparticles and zirconium dioxide nanoparticles.
5. The method for preparing the ceramic silicone rubber material with strong weather resistance according to claim 1, wherein the method comprises the following steps: the fluxing agent is selected from glass powder and/or zinc oxide.
6. The method for preparing high weather-resistant ceramic silicone rubber material according to claim 1, wherein: the flame retardant comprises a combination of aluminum hydroxide, magnesium hydroxide, a phosphorus-containing inorganic flame retardant and a phosphorus-containing organic flame retardant, and optionally, the mass ratio of the aluminum hydroxide to the magnesium hydroxide to the phosphorus-containing inorganic flame retardant to the phosphorus-containing organic flame retardant is (0.5-1) to (0.3-1) to (0.1-0.5).
7. The method for preparing high weather-resistant ceramic silicone rubber material according to claim 1, wherein: the platinum compound is chloroplatinic acid or a tetramethyldivinylsiloxane-platinum complex.
8. A preparation method of a ceramic silicone rubber tube with strong weather resistance is characterized by comprising the following steps:
s1: mixing the ceramic silicon rubber material by an internal mixer to obtain rubber compound;
s2: and putting the rubber compound into a mold of a vulcanizing machine for mold pressing, vulcanizing and shaping to obtain the ceramic silicone rubber tube.
9. The method for preparing the ceramic silicone rubber tube with strong weather resistance as claimed in claim 8, wherein the method comprises the following steps: the vulcanization temperature is 160-180 ℃, the vulcanization pressure is 2-5MPa, and the vulcanization time is 2-7 min.
10. The method for preparing the ceramic silicone rubber tube with strong weather resistance as claimed in claim 8, wherein the method comprises the following steps: the change rate of the tensile strength of the ceramic silicone rubber tube is 3-7%, and the change range of the hardness is 3-6Shore A.
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Application publication date: 20220902 Assignee: Zhejiang Baorui Applied Materials Co.,Ltd. Assignor: Zhejiang Baorun applied material Co.,Ltd. Contract record no.: X2024980006213 Denomination of invention: Preparation method of a ceramic silicone rubber material with strong weather resistance Granted publication date: 20230502 License type: Common License Record date: 20240524 |