CN114231036A - High-strength synergistic flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof - Google Patents
High-strength synergistic flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof Download PDFInfo
- Publication number
- CN114231036A CN114231036A CN202210016468.4A CN202210016468A CN114231036A CN 114231036 A CN114231036 A CN 114231036A CN 202210016468 A CN202210016468 A CN 202210016468A CN 114231036 A CN114231036 A CN 114231036A
- Authority
- CN
- China
- Prior art keywords
- silicone rubber
- parts
- temperature vulcanized
- retardant
- vulcanized silicone
- 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.)
- Granted
Links
- 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 198
- 239000003063 flame retardant Substances 0.000 title claims abstract description 164
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 140
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 124
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 239000002516 radical scavenger Substances 0.000 claims abstract description 23
- 239000006229 carbon black Substances 0.000 claims abstract description 20
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 20
- 229920002545 silicone oil Polymers 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 40
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 16
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 16
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 2
- YJTHBYQZDAVPJO-UHFFFAOYSA-N dimethyl(dioctoxy)stannane Chemical compound CCCCCCCCO[Sn](C)(C)OCCCCCCCC YJTHBYQZDAVPJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 20
- 239000004205 dimethyl polysiloxane Substances 0.000 abstract description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229920005573 silicon-containing polymer Polymers 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 238000007599 discharging Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910009819 Ti3C2 Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 239000012796 inorganic flame retardant Substances 0.000 description 6
- 230000000670 limiting effect Effects 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- UADBQCGSEHKIBH-UHFFFAOYSA-N 3-phenoxy-2,4-dihydro-1h-1,3,5,2,4,6-triazatriphosphinine Chemical compound P1N=PNPN1OC1=CC=CC=C1 UADBQCGSEHKIBH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 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
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 provides high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber and a preparation method thereof. The room temperature vulcanized silicone rubber is prepared from the following components in parts by weight: 100 parts of alpha, omega dihydroxy polydimethylsiloxane; 35-55 parts of calcium carbonate; 1-3 parts of white carbon black; 5-20 parts of dimethyl silicone oil; 10-20 parts of a flame retardant; 2-7 parts of a hydroxyl scavenging agent; 3-5 parts of a crosslinking agent; 2-6 parts of a coupling agent; 0.5-3 parts of a catalyst; the flame retardant comprises hexaphenoxycyclotriphosphazene and titanium carbide. According to the room temperature vulcanized silicone rubber, through optimization of the components, the dispersibility of the flame retardant in the silicone polymer can be improved, the addition amount of the flame retardant is reduced, the influence of the flame retardant on the mechanical property of the silicone rubber is reduced, the flame retardant grade of the silicone rubber can reach V-0 grade, and the room temperature vulcanized silicone rubber has the advantages of small addition amount of the flame retardant, high flame retardant efficiency, environmental friendliness, high strength, high elongation at break, simple preparation process and the like.
Description
Technical Field
The invention belongs to the technical field of silicon rubber, and particularly relates to high-strength synergistic flame-retardant room-temperature vulcanized silicon rubber and a preparation method thereof.
Background
The room temperature vulcanized silicone rubber is an organosilicon polymer with molecular chains composed of silicon oxygen atoms alternately, and two organic groups are usually connected on the silicon atoms, and the organosilicon polymer can be crosslinked into an elastomer with a three-dimensional network structure only by contacting with moisture in the air when in use. Room temperature vulcanized silicone rubber is used in the fields of building construction, electronic and electric appliances, transportation and transportation equipment, aerospace, chemical engineering and the like because of its excellent adhesion, electrical insulation, heat and cold resistance and chemical inertness. However, the flammability of silicone rubber itself and the generation of a large amount of toxic and harmful gases during combustion severely limit its application.
At present, people have conducted intensive research on flame retardance of silicone rubber, and although a large number of different types of flame retardants are used, the flame retardants have a certain flame retardance effect, but the flame retardants also have many defects. There are generally two methods for flame retarding silicone rubber materials: the first method is to blend the silicon rubber with an inorganic flame retardant to improve the flame retardant effect, but the addition of a large amount of the inorganic flame retardant can seriously affect the fluidity of the silicon rubber before curing and the mechanical properties of the silicon rubber after curing. For example: CN 112500707A discloses a high-efficiency flame-retardant silicone rubber and a preparation method and application thereof, aluminum hydroxide and a platinum flame retardant are compounded for flame retardance, and when the compounded flame retardant reaches 73.4 parts by mass, the prepared silicone rubber has a good flame-retardant effect; and the second is to use an organic flame retardant which has good flame retardant effect and excellent compatibility with the silicone rubber, so that the processing problem in the production process is avoided, and the influence on the mechanical property of the silicone rubber is small.
The existing flame retardant has no obvious flame retardant effect on the silicone rubber, and is often added in a large amount, but the mechanical property of the silicone rubber is obviously influenced by the excessive addition amount, so that the problems of low tensile strength, small elongation and the like are caused, and therefore, the development of the environment-friendly room temperature vulcanized silicone rubber with good flame retardancy and mechanical property has important application value.
Disclosure of Invention
Based on the above, the invention aims to provide the application of the flame retardant in the preparation of the silicone rubber, wherein the flame retardant can obviously improve the flame retardant efficiency and the mechanical property of the silicone rubber by adding a small amount of the flame retardant, and also has the smoke suppression effect.
The specific technical scheme is as follows:
the application of the flame retardant in preparation of the silicone rubber comprises hexaphenoxycyclotriphosphazene and titanium carbide, wherein the mass ratio of the hexaphenoxycyclotriphosphazene to the titanium carbide is (4: 6) - (6: 15).
In some embodiments, the mass ratio of the phenoxycyclotriphosphazene to the titanium carbide is (4: 6) - (7: 15).
In some of these embodiments, the silicone rubber is a room temperature vulcanizing silicone rubber.
The invention also provides the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The specific technical scheme is as follows:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber is prepared from the following components in parts by weight:
the flame retardant comprises hexaphenoxycyclotriphosphazene and titanium carbide, and the mass ratio of the hexaphenoxycyclotriphosphazene to the titanium carbide is (4: 6) - (6: 15).
In some embodiments, the mass ratio of the phenoxycyclotriphosphazene to the titanium carbide is (4: 6) - (7: 15).
In some embodiments, the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber is prepared from the following components in parts by weight:
the flame retardant comprises hexaphenoxycyclotriphosphazene and titanium carbide, and the mass ratio of the hexaphenoxycyclotriphosphazene to the titanium carbide is 5: 10.
in some of these embodiments, the calcium carbonate is selected from at least one of light calcium carbonate, activated calcium carbonate, and ground calcium carbonate.
In some of these embodiments, the calcium carbonate is selected from nano-active calcium carbonate.
In some of these embodiments, the nano-sized activated calcium carbonate has a specific surface area of 25m2/g～35m2/g。
In some of these embodiments, the white carbon black is selected from at least one of hydrophilic white carbon black and hydrophobic white carbon black.
In some embodiments, the white carbon black is hydrophobic white carbon black.
In some embodiments, the specific surface area of the hydrophobic silica is 150m2/g～200m2/g。
In some of these embodiments, the α, ω -dihydroxypolydimethylsiloxane comprises an α, ω -dihydroxypolydimethylsiloxane having a viscosity of 20000 to 30000 mPas and an α, ω -dihydroxypolydimethylsiloxane of 50000 to 60000 mPas, and the mass ratio of the α, ω -dihydroxypolydimethylsiloxane of 20000 to 30000 mPas to the α, ω -dihydroxypolydimethylsiloxane of 50000 to 60000 mPas is 1 (1 to 3).
In some of these embodiments, the dimethicone has a viscosity of from 300mPa s to 500mPa s.
In some of these embodiments, the hydroxyl scavenger is selected from at least one of vinyltrimethoxysilane, hexamethyldisilazane, an alkoxysilane, and a silazane.
In some of these embodiments, the hydroxyl scavenger is selected from hexamethyldisilazane.
In some of these embodiments, the crosslinking agent is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate, and propyl orthosilicate.
In some of these embodiments, the cross-linking agent is selected from methyl orthosilicate.
In some of these embodiments, the coupling agent is selected from at least one of gamma-aminopropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, and gamma-aminopropylmethyldiethoxysilane.
In some of these embodiments, the coupling agent is selected from gamma-aminopropylmethyldiethoxysilane.
In some of these embodiments, the catalyst is an organotin catalyst selected from at least one of dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dimethyltin dioctanolate.
In some of these embodiments, the organotin catalyst is dibutyltin dilaurate.
The invention also provides a preparation method of the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber, which comprises the following steps: s1, uniformly stirring the alpha, omega dihydroxy polysiloxane, calcium carbonate, white carbon black, hydroxyl scavenger and dimethyl silicone oil, then adding the flame retardant and continuously stirring to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber base material; adding a cross-linking agent into the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber base material, continuously stirring to obtain a mixed material, then adding the coupling agent and a catalyst into the mixed material, and continuously stirring to obtain a uniform material; and S2, curing the uniform material obtained in the step S1, and obtaining the synergistic flame-retardant room-temperature vulcanized silicone rubber after the curing is finished.
In some embodiments, the stirring is performed under vacuum condition, and the vacuum degree is-0.08 MPa to-0.10 MPa.
In some of these embodiments, the vacuum is-0.09 MPa.
In some embodiments, the stirring time of the alpha, omega dihydroxy polysiloxane, calcium carbonate, white carbon black, hydroxyl scavenging agent and dimethyl silicone oil is 3h to 5 h.
In some embodiments, the stirring time is 15min to 20min after the flame retardant is added continuously.
In some embodiments, the time for stirring after adding the cross-linking agent is 5min to 10 min.
In some embodiments, the stirring time after adding the silane coupling agent and the catalyst is 30min to 50 min.
In some embodiments, the curing temperature is 5-40 ℃ and the curing time is 14-28 d.
In some of the embodiments, the curing temperature is preferably 15-30 ℃.
The flame retardant consists of hexaphenoxycyclotriphosphazene and titanium carbide (Ti)3C2) Synergistic compounding is carried out. The hexaphenoxycyclotriphosphazene flame retardant can generate compounds such as phosphoric acid and metaphosphoric acid at high temperature, and the compounds are favorable for forming a more compact carbon layer, so that the release of toxic volatile matters and the permeation of oxygen are inhibited. The compact carbon layer generated by the combustion of the hexaphenoxycyclotriphosphazene flame retardant can also prevent heat from being transmitted to the interior of the silicon rubber material, and effectively prevent the interior polymer from being further degraded, so that the release amount of toxic volatile matters is reduced. Ti3C2As the inorganic flame retardant, Ti is added at the initial stage of combustion3C2The decomposition reaction generated by heating can absorb a large amount of latent heat, so that the actual temperature of the surface of the silicon rubber is reduced, the rate of the silicon rubber degrading into low molecules is slowed, and the generation of combustible substances is reduced. With the continuous progress of combustion, the hexaphenoxycyclotriphosphazene on one hand pyrolyzes to generate a phosphorus-containing gaseous product and a phosphorus-containing free radical to capture combustion free radicals such as H, HO and the like, and on the other hand, the phosphorus-containing group generated at high temperature can promote silicon rubber and Ti3C2The charring amount of the coal is increased. At the same time, the coke can capture Ti3C2Large amount of metal oxide TiO generated by pyrolysis2The strength of the carbon layer is further improved, thereby more effectively blocking the transfer of oxygen, heat or combustible gas. In addition to that, Ti3C2Can be thermally decomposed into TiO under the condition of oxygen2And carbon nanosheet, TiO2Attached to the carbon nanosheets. And TiO 22Is a lewis acid, which is typically a solid acid catalyst. The solid acid has a catalytic effect in the polymer degradation process, and can promote the conversion of low carbon generated in the pyrolysis process into a graphitized carbon layer. In addition, a large amount of small-sized carbon residues generated during the combustion process are deposited on Ti3C2On the surface, a compact protective carbon layer is formed, and the exchange of heat and substances in the combustion process is delayed. Ti3C2Decomposed into catalytic TiO by heating2It also promotes the reduction of toxic gases and increases the fire safety of the polymer. In addition to that, Ti3C2The two-dimensional structure can be fully contacted with the silicon rubber, and the surface of the two-dimensional structure contains a large amount of-OH and-O-, which can enable the titanium carbide and the silicon rubber to form firmer chemical bonds, thereby enhancing the mechanical property of the silicon rubber. Thus, hexaphenoxycyclotriphosphazene with Ti3C2The synergistic use of the components not only can greatly improve the flame retardant efficiency and the mechanical property of the silicon rubber, but also has the smoke suppression effect.
Further, the invention also optimizes and obtains the room temperature vulcanized silicone rubber containing the flame retardant, which is prepared by adopting alpha, omega dihydroxy polysiloxane, calcium carbonate, white carbon black, dimethyl silicone oil, hydroxyl scavenging agent, the flame retardant, cross-linking agent and coupling agent in an alcohol type system. In one aspect, Ti in the flame retardant3C2A compact carbon layer can be generated in the combustion process to block the transmission of heat and combustible gas, and the rich Zn element also has a certain smoke suppression effect; on the other hand, hexaphenoxycyclotriphosphazene can generate phosphorus-containing gaseous products and phosphorus-containing free radicals under the pyrolysis condition, capture combustion free radicals such as H, HO and the like, and release abundant N elements in molecules at high temperatureThe flame-retardant ammonia gas is used for diluting oxygen and combustible gas, so that the flame retardant fully plays a flame-retardant role in a gas phase; in addition, phosphorus-containing groups generated by hexaphenoxycyclotriphosphazene at high temperature promote silicon rubber and Ti3C2The charring of the coke increases the burning charring amount, and meanwhile, the coke can capture Ti3C2A large amount of metallic oxide ZnO generated by pyrolysis further improves the strength of the carbon layer, promotes the silicon rubber to generate more compact residues, and enables the flame retardant to fully play a flame retardant role in a condensed phase. Alpha, omega dihydroxy polysiloxane as basic polymer has no practical value under the assistance of no reinforcing filler, calcium carbonate and white carbon black play a role in reinforcement, and the flame retardant also has a certain reinforcing role, and the components can improve the mechanical property of the silicone rubber and also have certain functions of adjusting consistency and flame retardance through compounding in proper proportion; the dimethyl silicone oil can be used as a plasticizer to greatly optimize the processability of the synergistic flame-retardant room-temperature vulcanized silicone rubber in the synthetic process; the addition of the flame retardant can enable the silicone rubber to have excellent flame retardant performance; the hydroxyl scavenger can remove redundant hydroxyl in the basic polymer, so that the vulcanization in the processing and preparation process is avoided; the cross-linking agent can promote the vulcanization molding of the basic polymer to form a three-dimensional network structure, so that the strength and the elasticity of the silicone rubber are improved; the silane coupling agent can reduce the agglomeration between the base polymer and the inorganic material; the catalyst promotes the vulcanization effect, shortens the vulcanization time and improves the vulcanization efficiency. Through the mutual matching of the components, the dispersibility of the flame retardant in the silicone polymer can be improved, the addition of the flame retardant is reduced, the influence of the flame retardant on the mechanical property of the silicone rubber is reduced, the flame retardant grade of the silicone rubber can reach V-0 grade, and the room-temperature vulcanized silicone rubber has the advantages of small addition of the flame retardant, high flame retardant efficiency, environmental friendliness, high strength, high elongation at break, simple preparation process, less smoke and less toxic gas in the preparation process and the like.
Drawings
FIG. 1 is a digital photograph of the vertical burning process of the high strength synergistic flame retardant room temperature vulcanized silicone rubber of example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the carbon residue after combustion of the high strength synergistic flame retardant room temperature vulcanized silicone rubber of example 1.
Detailed Description
Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The molecular structure of the hexaphenoxycyclotriphosphazene is as follows:
example 1:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypoly having a viscosity of 25000 mPasDimethylsiloxane, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white and 45 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Example 2:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white and 35 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Example 3:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white and 55 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Example 4:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white and 45 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 4 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; the synergistic flame-retardant room-temperature vulcanized silicone rubber base material and 3 parts of methyl orthosilicate cross-linking agent are mixed inAnd (3) carrying out vacuum mixing in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing to carry out vacuum mixing for 35min, discharging, and injecting the mixture into a polytetrafluoroethylene mold to carry out vulcanization for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Example 5:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white and 45 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 6 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Example 6:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Perg fumed silica and 45 parts of activated calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisiloxaneAdding an azanyl hydroxyl scavenger into a power kneading machine, vacuumizing and mixing for 4h at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 15 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30min at 100 ℃ to obtain the synergistic flame retardant room temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Comparative example 1:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber of the comparative example comprises the following preparation raw materials (in parts by weight) and steps:
adding 50 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 25000 mPas, 50 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 55000 mPas, 45 parts of activated calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPas and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃ to obtain the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Comparative example 2:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber of the comparative example comprises the following preparation raw materials (in parts by weight) and steps:
mixing 50 parts of viscosity25000 mPas alpha, omega dihydroxypolydimethylsiloxane, 50 parts of 55000 mPas alpha, omega dihydroxypolydimethylsiloxane, 2 parts of 180m specific surface area2Adding the silica white and 30 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Comparative example 3:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber of the comparative example comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white, 60 parts of active calcium carbonate, 5 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Comparative example 4:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber of the comparative example comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white, 45 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500mPa & s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 15 parts of titanium carbide as a flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame-retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Comparative example 5:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber of the comparative example comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white, 45 parts of activated calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 15 parts of hexaphenoxycyclotriphosphazene serving as a flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame-retardant room-temperature vulcanized silicone rubber base material; a synergistic flame-retardant room-temperature vulcanized silicone rubber base material and 3 parts of methyl orthosilicate cross-linking agent are added into a planetary machineAnd (3) carrying out medium vacuum mixing for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing carrying out vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing at 25 ℃ for 21 days to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Comparative example 6:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber of the comparative example comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Adding the silica white and 45 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxyl scavenger into a power kneader, vacuumizing and mixing for 4 hours at 130 ℃, then adding 7 parts of hexaphenoxycyclotriphosphazene and 10 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30 minutes at 100 ℃, and obtaining the synergistic flame retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
Comparative example 7:
the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber of the comparative example comprises the following preparation raw materials (in parts by weight) and steps:
50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 25000 mPas, 50 parts of an alpha, omega-dihydroxypolydimethylsiloxane having a viscosity of 55000 mPas, 2 parts of a specific surface area of 180m2Perg fumed silica and 45 parts of active calcium carbonate, 10 parts of dimethyl silicone oil with the viscosity of 500 mPa.s and 3 parts of hexamethyldisilazane hydroxysilaneAdding the base scavenging agent into a power kneader, vacuumizing and mixing for 4h at 130 ℃, then adding 5 parts of hexaphenoxycyclotriphosphazene and 18 parts of titanium carbide compound flame retardant, vacuumizing and mixing for 30min at 100 ℃ to obtain the synergistic flame-retardant room-temperature vulcanized silicone rubber base material; vacuum mixing the synergistic flame-retardant room-temperature vulcanized silicone rubber base material with 3 parts of methyl orthosilicate cross-linking agent in a planetary machine for 8min, finally adding 4 parts of gamma-aminopropyl methyl diethoxysilane and 1.5 parts of dibutyltin dilaurate catalyst, continuing vacuum mixing for 35min, discharging, injecting the mixture into a polytetrafluoroethylene mold, and vulcanizing for 21 days at 25 ℃ to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber.
The vacuum degree in the preparation steps is-0.09 MPa.
And (3) performance testing:
the performance tests of examples 1-6 and comparative examples 1-7 were conducted, wherein:
tensile strength and elongation at break: the test is carried out according to the determination of the tensile stress strain performance of GB/T528-2009 vulcanized rubber or thermoplastic rubber;
limiting Oxygen Index (LOI): the test is carried out according to the GB/T10707-2008 rubber combustion performance measurement;
vertical combustion (UL-94): the test is carried out according to GB/T24267-2009 flame-retardant sealant for buildings.
The results are shown in table 1:
TABLE 1 Performance test results of Room temperature vulcanized Silicone rubbers of examples 1 to 6 and comparative examples 1 to 7
| Project testing | Tensile strength/MPa | Elongation at break/% | LOI/％ | UL94 |
| Example 1 | 2.93 | 318 | 28.7 | FV-0 |
| Example 2 | 2.68 | 322 | 27.6 | FV-0 |
| Example 3 | 2.79 | 253 | 28.9 | FV-0 |
| Example 4 | 2.88 | 321 | 28.2 | FV-0 |
| Example 5 | 2.72 | 308 | 27.1 | FV-1 |
| Example 6 | 2.66 | 269 | 28.8 | FV-0 |
| Comparative example 1 | 1.84 | 238 | 28.0 | FV-0 |
| Comparative example 2 | 2.55 | 328 | 27.2 | FV-1 |
| Comparative example 3 | 2.77 | 241 | 27.8 | FV-0 |
| Comparative example 4 | 2.85 | 311 | 26.8 | FV-1 |
| Comparative example 5 | 2.73 | 324 | 26.1 | FV-1 |
| Comparative example 6 | 2.64 | 334 | 26.8 | FV-1 |
| Comparative example 7 | 2.86 | 270 | 28.7 | FV-0 |
The results in Table 1 show that the room temperature vulcanized silicone rubber optimally obtained by the invention (examples 1-6) has good flame retardant effect, high tensile strength and elongation at break. Among them, the high strength synergistic flame retardant room temperature vulcanized silicone rubber of example 1 has the best performance, the digital photograph of the vertical burning process is shown in fig. 1, and the Scanning Electron Microscope (SEM) image of the carbon residue after burning is shown in fig. 2.
Compared with the embodiment 1, the room temperature vulcanized silicone rubber of the comparative example 1 is not added with the white carbon black, so that the tensile strength and the elongation at break of the room temperature vulcanized silicone rubber are obviously reduced, because the free hydroxyl on the surface of the white carbon black and silicone rubber molecules form physical or chemical combination, and a silicone rubber molecule adsorption layer is formed on the surface of the white carbon black to form a three-dimensional network structure in which white carbon black particles and the silicone rubber molecules are connected into a whole, thereby playing a reinforcing role. The tensile strength and elongation at break of comparative example 1, in which no white carbon black was added, were significantly reduced.
The comparative example 2, in which the weight part of activated calcium carbonate in the room temperature vulcanized silicone rubber was reduced to 30 parts, resulted in a significant decrease in tensile strength and limiting oxygen index, and the vertical burning grade became FV-1, compared to example 1. This is mainly because, after the amount of calcium carbonate is reduced, the filler reinforcing effect of the room temperature vulcanized silicone rubber is reduced, and the tensile properties are reduced. And calcium carbonate itself also has flame retardant properties, so when the amount of calcium carbonate added is reduced, the flame retardant properties are also reduced.
In comparison with example 1, comparative example 3, in which the added part of the activated calcium carbonate was 60 parts and the added part of the dimethylsilicone fluid was 5 parts, resulted in a significant decrease in tensile strength and elongation at break thereof, because when the added amount of calcium carbonate was excessive, the relative amount of the base rubber was decreased, thereby resulting in that the calcium carbonate was not easily uniformly dispersed in the base rubber. And with the increase of the calcium carbonate content, the strength of the room-temperature vulcanized silicone rubber before and after aging is also reduced at an accelerated speed.
Compared with the example 1, the room temperature vulcanized silicone rubber of the comparative example 4 singly uses titanium carbide as a flame retardant, and the room temperature vulcanized silicone rubber of the comparative example 5 singly uses hexaphenoxycyclotriphosphazene as a flame retardant, so that the tensile strength and the limiting oxygen index of the room temperature vulcanized silicone rubber prepared by the two are obviously reduced, and the vertical burning grade is changed into FV-1. The demonstration shows that when titanium carbide or hexaphenoxycyclotriphosphazene is singly used as the flame retardant, no synergistic effect can be generated among the flame retardants, and the flame retardant effect is not obvious. In addition, the hexaphenoxycyclotriphosphazene is used as an organic flame retardant, so that the dispersibility of the flame retardant in a base polymer can be increased, and the agglomeration of the filler and the inorganic flame retardant is reduced, so that the tensile property of the room-temperature vulcanized silicone rubber is improved.
Compared with the example 1, the addition part of the hexaphenoxycyclotriphosphazene of the flame retardant of the comparative example 6 is 7 parts, and the addition part of the titanium carbide of the flame retardant of the comparative example 7 is 18 parts, so that the mass ratio of the hexaphenoxycyclotriphosphazene to the titanium carbide is changed and is not in the mass ratio range of the invention. Wherein the tensile strength and the limiting oxygen index of the room temperature vulcanized silicone rubber prepared in the comparative example 6 are obviously reduced, and the vertical burning grade is changed into FV-1; the elongation at break of the room temperature vulcanized silicone rubber prepared in the comparative example 7 is obviously reduced, which shows that the mechanical property and the flame retardant property can be exerted only by the compounding of the organic flame retardant hexaphenoxycyclotriphosphazene and the inorganic flame retardant titanium carbide within a certain proportion range. When the amount of the organic flame retardant or the inorganic flame retardant is too large, the respective properties of the room temperature vulcanized silicone rubber are adversely affected.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The application of the flame retardant in preparation of the silicone rubber is characterized in that the flame retardant comprises hexaphenoxycyclotriphosphazene and titanium carbide, and the mass ratio of the hexaphenoxycyclotriphosphazene to the titanium carbide is (4: 6) - (6: 15).
2. The high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber is characterized by being prepared from the following components in parts by weight:
the flame retardant comprises hexaphenoxycyclotriphosphazene and titanium carbide, and the mass ratio of the hexaphenoxycyclotriphosphazene to the titanium carbide is (4: 6) - (5: 15).
3. The high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber according to claim 2, which is prepared from the following components in parts by weight:
the flame retardant comprises hexaphenoxycyclotriphosphazene and titanium carbide, and the mass ratio of the hexaphenoxycyclotriphosphazene to the titanium carbide is 5: 10.
4. the high strength synergistic flame retardant room temperature vulcanized silicone rubber according to claim 2, wherein the calcium carbonate is at least one selected from the group consisting of light calcium carbonate, activated calcium carbonate and heavy calcium carbonate.
5. The high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber according to claim 2, wherein the white carbon black is at least one selected from hydrophilic white carbon black and hydrophobic white carbon black.
6. The high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber according to claim 2, wherein the viscosity of the dimethylsilicone fluid is 300 to 500 mPa-s.
7. The high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber according to claim 2, wherein the α, ω -dihydroxypolydimethylsiloxane comprises α, ω -dihydroxypolydimethylsiloxane having a viscosity of 20000 mPa-s to 30000 mPa-s and α, ω -dihydroxypolydimethylsiloxane of 50000 mPa-s to 60000 mPa-s, and a mass ratio of the α, ω -dihydroxypolydimethylsiloxane of 20000 mPa-s to 30000 mPa-s to the α, ω -dihydroxypolydimethylsiloxane of 50000 mPa-s to 60000 mPa-s is 1 (1) to 3);
and/or, the hydroxyl scavenger is selected from at least one of vinyl trimethoxy silane, hexamethyl disilazane, alkoxy silane and silazane;
and/or the cross-linking agent is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate;
and/or the coupling agent is selected from at least one of gamma-aminopropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane and gamma-aminopropylmethyldiethoxysilane;
and/or the catalyst is an organic tin catalyst, and the organic tin catalyst is at least one of dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate and dimethyltin dioctanolate.
8. The method for preparing the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber according to any one of claims 2 to 7, characterized by comprising the following steps: s1, uniformly stirring the alpha, omega dihydroxy polysiloxane, calcium carbonate, white carbon black, hydroxyl scavenger and dimethyl silicone oil, then adding the flame retardant and continuously stirring to obtain the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber base material; adding a cross-linking agent into the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber base material, continuously stirring to obtain a mixed material, then adding the coupling agent and a catalyst into the mixed material, and continuously stirring to obtain a uniform material; and S2, curing the uniform material obtained in the step S1, and obtaining the synergistic flame-retardant room-temperature vulcanized silicone rubber after the curing is finished.
9. The method for preparing the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber according to claim 8, wherein the stirring is carried out under a vacuum condition, and the vacuum degree is-0.08 MPa to-0.10 MPa;
and/or the stirring time of the alpha, omega dihydroxy polysiloxane, calcium carbonate, white carbon black, hydroxyl scavenger and dimethyl silicone oil is 3 to 5 hours;
and/or adding the flame retardant and stirring for 15-20 min after continuing;
and/or, the cross-linking agent is added and stirred for 5min to 10 min;
and/or adding the silane coupling agent and the catalyst and stirring for 30-50 min.
10. The method for preparing the high-strength synergistic flame-retardant room-temperature vulcanized silicone rubber according to claim 8, wherein the curing temperature is 5-40 ℃ and the curing time is 14-28 d.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210016468.4A CN114231036B (en) | 2022-01-07 | 2022-01-07 | High-strength synergistic flame-retardant room temperature vulcanized silicone rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210016468.4A CN114231036B (en) | 2022-01-07 | 2022-01-07 | High-strength synergistic flame-retardant room temperature vulcanized silicone rubber and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114231036A true CN114231036A (en) | 2022-03-25 |
| CN114231036B CN114231036B (en) | 2023-07-21 |
Family
ID=80745998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210016468.4A Active CN114231036B (en) | 2022-01-07 | 2022-01-07 | High-strength synergistic flame-retardant room temperature vulcanized silicone rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114231036B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160787A (en) * | 2022-07-21 | 2022-10-11 | 上海熹贾精密技术有限公司 | Flame-retardant room-temperature vulcanized silicone rubber |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312815A (en) * | 1998-08-13 | 2001-09-12 | 大塚化学株式会社 | Cross-linked phenoxyphosphazene compound, process for producing same, flame retardant, flame-retar dant resin composition and molded flame-retardent resin |
| CN1313877A (en) * | 1998-08-26 | 2001-09-19 | 大塚化学株式会社 | Powdery flame retardent |
| CN108003628A (en) * | 2017-12-28 | 2018-05-08 | 唐山师范学院 | Fire-retardant room temperature vulcanized silicone rubber and preparation method thereof |
| CN112839949A (en) * | 2018-10-09 | 2021-05-25 | 大塚化学株式会社 | Cyclic phosphazene compound, flame retardant for resin, resin composition containing same, and molded article thereof |
| CN113087969A (en) * | 2021-04-02 | 2021-07-09 | 应急管理部四川消防研究所 | Reactive flame-retardant ceramic powder and ceramic organic silicon elastomer reinforced and flame-retardant by using same |
| CN114507380A (en) * | 2022-01-24 | 2022-05-17 | 华南理工大学 | MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof |
| CN115418089A (en) * | 2022-09-07 | 2022-12-02 | 浙江唐风工艺品有限公司 | Polylactic acid modifier and stretch-proof high-strength modified polylactic acid |
| CN115466417A (en) * | 2022-07-28 | 2022-12-13 | 武汉大学 | MXene/polyphosphazene-based flexible electrode material and preparation method and application thereof |
-
2022
- 2022-01-07 CN CN202210016468.4A patent/CN114231036B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312815A (en) * | 1998-08-13 | 2001-09-12 | 大塚化学株式会社 | Cross-linked phenoxyphosphazene compound, process for producing same, flame retardant, flame-retar dant resin composition and molded flame-retardent resin |
| CN1313877A (en) * | 1998-08-26 | 2001-09-19 | 大塚化学株式会社 | Powdery flame retardent |
| CN108003628A (en) * | 2017-12-28 | 2018-05-08 | 唐山师范学院 | Fire-retardant room temperature vulcanized silicone rubber and preparation method thereof |
| CN112839949A (en) * | 2018-10-09 | 2021-05-25 | 大塚化学株式会社 | Cyclic phosphazene compound, flame retardant for resin, resin composition containing same, and molded article thereof |
| CN113087969A (en) * | 2021-04-02 | 2021-07-09 | 应急管理部四川消防研究所 | Reactive flame-retardant ceramic powder and ceramic organic silicon elastomer reinforced and flame-retardant by using same |
| CN114507380A (en) * | 2022-01-24 | 2022-05-17 | 华南理工大学 | MXene nanosheet modified phosphorus-nitrogen single-component intumescent flame retardant and preparation method and application thereof |
| CN115466417A (en) * | 2022-07-28 | 2022-12-13 | 武汉大学 | MXene/polyphosphazene-based flexible electrode material and preparation method and application thereof |
| CN115418089A (en) * | 2022-09-07 | 2022-12-02 | 浙江唐风工艺品有限公司 | Polylactic acid modifier and stretch-proof high-strength modified polylactic acid |
Non-Patent Citations (5)
| Title |
|---|
| YUYANG ZHOU等: "DOPO-Decorated Two-Dimensional MXene Nanosheets for Flame-Retardant, Ultraviolet-Protective, and Reinforced Polylactide Composites", 《ACS APPL. MATER. INTERFACES》 * |
| YUYANG ZHOU等: "DOPO-Decorated Two-Dimensional MXene Nanosheets for Flame-Retardant, Ultraviolet-Protective, and Reinforced Polylactide Composites", 《ACS APPL. MATER. INTERFACES》, 3 May 2021 (2021-05-03), pages 21876 - 21887 * |
| 丁绍兰等: "《革制品材料学》", 31 January 2019, pages: 215 * |
| 李梦琪等: "纳米材料阻燃聚乳酸的研究进展", 《中国塑料》 * |
| 李梦琪等: "纳米材料阻燃聚乳酸的研究进展", 《中国塑料》, 30 April 2022 (2022-04-30), pages 102 - 114 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160787A (en) * | 2022-07-21 | 2022-10-11 | 上海熹贾精密技术有限公司 | Flame-retardant room-temperature vulcanized silicone rubber |
| CN115160787B (en) * | 2022-07-21 | 2023-09-19 | 上海熹贾精密技术有限公司 | Flame-retardant room temperature vulcanized silicone rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114231036B (en) | 2023-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111378285B (en) | High-strength high-flame-retardant organic silicon foam material and preparation method thereof | |
| CN109627770B (en) | Dealcoholized condensed type double-component room temperature vulcanized silicone rubber and preparation method thereof | |
| CN109679572B (en) | Low-modulus high-displacement-capacity silicone fireproof sealant and preparation method thereof | |
| CN106833478B (en) | High-performance flame-retardant two-component silane modified polyether sealant and preparation method thereof | |
| KR102043429B1 (en) | Silicone rubber composition and Cured product thereof | |
| CN110982480B (en) | Single-component flame-retardant high-temperature-resistant silicone sealant and preparation method thereof | |
| CN114774070B (en) | Low-smoke-amount silicone flame-retardant sealant and preparation method thereof | |
| KR101896898B1 (en) | Silicone rubber composition with fire resistant | |
| JP2007197735A (en) | Compound which may be crosslinked to give elastomer with cleavage of alcohol from alkoxysilyl end group | |
| CN114045151B (en) | Flame-retardant silicone sealant and preparation method thereof | |
| JP4843200B2 (en) | Process for producing organopolysiloxane materials crosslinkable to elastomers | |
| CN106084236B (en) | A kind of room temperature vulcanized sili cone rubber and its crosslinking agent | |
| CN114231041A (en) | B1-grade flame-retardant ceramic low-smoke silicone rubber cable material and preparation method thereof | |
| CN110577747A (en) | room temperature vulcanized fluorosilicone rubber and preparation method thereof | |
| CN107936908A (en) | Silicone sealant | |
| CN109251721B (en) | Sealant and preparation method thereof | |
| CN107699188A (en) | A kind of transparent high temperature resistant flame-proof silicone sealant and preparation method | |
| CN114106768A (en) | Bi-component flame-retardant silicone sealant and preparation method thereof | |
| CN114231036B (en) | High-strength synergistic flame-retardant room temperature vulcanized silicone rubber and preparation method thereof | |
| CN114958292A (en) | Fireproof sealant and preparation method thereof | |
| CN116083040A (en) | High-strength fireproof sealant and preparation method thereof | |
| CN112778765A (en) | Composite flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof | |
| CN112063181A (en) | Mixing silicone rubber and preparation method thereof | |
| CN111073298A (en) | Flame-retardant plugging agent for substation and preparation method and use method thereof | |
| DE4136689A1 (en) | Curable siloxane sealant for multi-pane insulating glass unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Guangzhou private science and Technology Park Yunan road Baiyun District of Guangzhou City, Guangdong Province, No. 1 510540 Patentee after: Guangzhou Baiyun Technology Co.,Ltd. Patentee after: Guangdong Baiyun Technology Co.,Ltd. Address before: Guangzhou private science and Technology Park Yunan road Baiyun District of Guangzhou City, Guangdong Province, No. 1 510540 Patentee before: GUANGZHOU BAIYUN CHEMICAL INDUSTRY Co.,Ltd. Patentee before: Guangdong Baiyun Technology Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |