CN109354878A - The duplex metal hydroxide nanometer piece and the preparation method and application thereof of organic ceramic presoma modification - Google Patents
The duplex metal hydroxide nanometer piece and the preparation method and application thereof of organic ceramic presoma modification Download PDFInfo
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- CN109354878A CN109354878A CN201810874763.7A CN201810874763A CN109354878A CN 109354878 A CN109354878 A CN 109354878A CN 201810874763 A CN201810874763 A CN 201810874763A CN 109354878 A CN109354878 A CN 109354878A
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- metal hydroxide
- organic ceramic
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- ceramic presoma
- modification
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- 239000000919 ceramic Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 43
- 230000004048 modification Effects 0.000 title claims abstract description 43
- 238000012986 modification Methods 0.000 title claims abstract description 43
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 33
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 84
- 229920001971 elastomer Polymers 0.000 claims abstract description 53
- 239000005060 rubber Substances 0.000 claims abstract description 53
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 42
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 24
- 238000010792 warming Methods 0.000 claims abstract description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- 238000013019 agitation Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 229910000077 silane Inorganic materials 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 235000019241 carbon black Nutrition 0.000 claims description 10
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 238000010074 rubber mixing Methods 0.000 claims description 9
- 238000004073 vulcanization Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 7
- 229920000260 silastic Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 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 6
- 238000000034 method Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005411 Van der Waals force Methods 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 230000003993 interaction Effects 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- HHRKFGMMAHZWIM-UHFFFAOYSA-N ethenoxyboronic acid Chemical compound OB(O)OC=C HHRKFGMMAHZWIM-UHFFFAOYSA-N 0.000 claims 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 44
- 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 abstract description 33
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 69
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000009830 intercalation Methods 0.000 description 10
- 230000002687 intercalation Effects 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000013112 stability test Methods 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000012700 ceramic precursor Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- WBCLZGYCULJPDT-UHFFFAOYSA-N 2-tert-butylperoxy-2,5-dimethylhexane Chemical compound CC(C)CCC(C)(C)OOC(C)(C)C WBCLZGYCULJPDT-UHFFFAOYSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910019092 Mg-O Inorganic materials 0.000 description 1
- 229910019395 Mg—O Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- OUFRIWNNMFWZTM-UHFFFAOYSA-M sodium arsanilate Chemical compound [Na+].NC1=CC=C([As](O)([O-])=O)C=C1 OUFRIWNNMFWZTM-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses the duplex metal hydroxide nanometer pieces and the preparation method and application thereof of organic ceramic presoma modification.The preparation method is boric acid, alkoxy silane and vinylsiloxane to be added in reaction kettle, and organic solvent and catalyst is added, and is stirred evenly at 25~45 DEG C；70~95 DEG C of 2~5h of pre-polymerization are warming up to, then are warming up to 140~160 DEG C of 2~5h of reaction；Obtain the organic ceramic presoma containing sulfonate radical and vinyl；Organic ceramic presoma, double-metal hydroxide and dehydrated alcohol containing sulfonate radical and vinyl are mixed, ultrasonic agitation obtains white suspension；55~60 DEG C of 2~4h of reaction.Product prepared by the present invention is good with rubber compatibility, is easily dispersed, and has excellent thermal stability and flame retardant property；Only small amount (≤5phr), which need to be added, can effectively improve the flame retardant property and thermal stability of silicon rubber.
Description
Technical field
The present invention relates to the preparation and application fields of polymer halogen-free flame retardants, more particularly, to a kind of organic ceramic forerunner
The duplex metal hydroxide nanometer piece and the preparation method and application thereof of body modification.
Background technique
A kind of nano-meter flame retardants of the layered double hydroxide (LDH) as novel environment friendly have obtained quickly in recent years
Development.LDH is by certain proportion trivalent and divalent metal as main body lamella, and anion fills the layer stylolitization of interlayer
Object is closed, lamella and interlayer anion mainly pass through Van der Waals force and electrostatic force combines.The lamellar structure of LDH has certain resistance
It is decomposed when effect, high temperature and generates water and metal oxide, take away heat, dilution oxygen and fuel gas.But LDH exists layer by layer
Stacked structure only can not make it evenly dispersed in a polymer matrix by mechanical blending, meeting its flame-retarded efficiency of extreme influence
It plays.The compatibility of itself and polymeric matrix can be improved by carrying out intercalation modifying to LDH, improve flame retardant effect, common intercalation
Modifying agent is anionic surfactant, such as lauryl sulfate.Qiu etc. is prepared for using solution facture (AMOST)
The LDH (SDS-LDH) of the dodecyl sulphate intercalation and LDH (Stearic-LDH) of stearic acid intercalation improves LDH poly-
Dispersibility (Qiu L, Gao Y S, Lu P, et al.Synthesis and properties of in propylene (PP) matrix
polypropylene/layered double hydroxide nanocomposites with different LDHs
particle sizes[J].Journal of Applied Polymer Science,2018,135(18):46204.).So
And dodecyl sodium sulfonate and stearic thermal stability are poor, and are readily burned, therefore, prepared LDH flame retardant effect is not
It is ideal.106674598 A of Chinese invention patent application CN carries out intercalation modifying to LDH using dodecyl sodium sulfate, then exists
Interlayer introduces phosphonium flame retardant BHPPO, improves the flame retarding efficiency of LDH to a certain extent, but thermal stability is still needed into one
Step improves.
Organic ceramic presoma, which refers in high temperature or burning, mainly to include organic metal with the fire retardant substance of ceramic
Compound, polysilazane, Polycarbosilane, polyborosiloxane etc..Wherein, polyborosiloxane is a kind of novel organic ceramic forerunner
Body contains the higher B-O key of bond energy and Si-O key in main chain, and there are p- π and d- are pi-conjugated in structure, thus has excellent
High temperature resistance and flame retardant property, show huge application prospect.Zhou Wenjun etc. is with dimethyldimethoxysil,ne, hexichol
Base dimethoxysilane and boric acid are that primary raw material uses two-step method to be prepared for polyborosiloxane fire retardant, and is applied to poly-
Carbonic ester (PC) is fire-retardant, and (Zhou Wenjun, Song Jian, Chen Youcai wait the synthesis technology of polyborosiloxane fire retardant and its in polycarbonate
In application [J] Journal of Chemical Industry and Engineering, 2012,63 (10): 3365-3371.), research find addition 5% (mass fraction) poly- borosilicate
For the PC composite material limit oxygen index (LOI) of oxygen alkane up to 39.4%, purer PC improves 52%.But the poly- boron of this method synthesis
Without chemical bond between siloxanes and PC matrix, compatibility is poor, need to further improve.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of existing LDH method of modifying, it is good to provide a kind of thermal stability, and flame retardant effect is aobvious
The duplex metal hydroxide nanometer piece of organic ceramic precursor modification is write, and is used for flame-proof silicon rubber.
It is a further object of the present invention to provide a kind of duplex metal hydroxide nanometer pieces of organic ceramic precursor modification
Preparation method.
Further object of the present invention is to provide a kind of duplex metal hydroxide nanometer piece of organic ceramic precursor modification
Using.
In view of the problems of the existing technology, the present invention with boric acid, alkoxy silane and vinyl silanes etc. for raw material, with
H2SO4Deng for catalyst, the organic ceramic presoma (OCP) containing sulfonate radical and vinyl is obtained by polycondensation reaction；Then use
OCP to double-metal hydroxide (LDH) carry out intercalation modification, prepare OCP modify LDH nanometer sheet (OCP-d-LDH), and by its
It is introduced into silicon rubber (SR), is prepared for flame retardant property and heat resistance silastic material outstanding.The present invention is by synthesizing one kind
Organic ceramic presoma (OCP) containing sulfonate radical and vinyl, and it is used for modification LDH.On the one hand, the introducing of OCP can be with
The interlamellar spacing for increasing LDH makes it have preferably dispersibility in silicone rubber matrix；On the other hand, can effectively play LDH and
The synergistic effect of OCP improves the flame retardant property and thermal stability of silicon rubber；Meanwhile vinyl can be with silicon rubber strand
Effect is crosslinked, the compatibility of LDH and silicon rubber are increased.OCP-d-LDH prepared by the present invention is good with rubber compatibility,
It is easily dispersed, there is excellent thermal stability and flame retardant property；Only small amount (≤5phr), which need to be added, can effectively improve silicon
The flame retardant property and thermal stability of rubber, prepared SR/OCP-d-LDH material can be widely applied to electronic apparatus, space flight
The fields such as aviation, auto industry.
The purpose of the present invention can be achieved through the following technical solutions:
The preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification, comprising the following steps:
(1) preparation of the organic ceramic presoma containing sulfonate radical and vinyl
Boric acid, alkoxy silane and vinylsiloxane are added in reaction kettle, and organic solvent and catalyst is added,
It is stirred at 25~45 DEG C, is sufficiently mixed reactant uniformly；70~95 DEG C of 2~5h of pre-polymerization are warming up to, then are warming up to 140~160
DEG C reaction 2~5h；It is cooled to room temperature after reaction；After washing, vacuum rotary steam, vacuum drying, obtain containing sulfonate radical and
The organic ceramic presoma of vinyl；Controlling boron atom and the control of silicon atom molar ratio is B:Si=1:4~1:7；Alkoxyl silicone
Alkane and vinyl silanes molar ratio are 1:1~3:1；The catalyst is one or both of sulfuric acid and p-methyl benzenesulfonic acid；
(2) preparation of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification
Organic ceramic presoma, double-metal hydroxide and dehydrated alcohol containing sulfonate radical and vinyl are mixed, surpassed
Sound stirring keeps its fully dispersed, then with magnetic agitation, obtains white suspension；55~60 DEG C of 2~4h of reaction, vacuum rotary steam, very
The duplex metal hydroxide nanometer piece of organic ceramic presoma modification is obtained after sky is dry；Its structure of the double-metal hydroxide
General formula are as follows: [MⅡ 1‐xMⅢ x(OH)2]x+(Am‐)x/m·nH2O, wherein x=0.17~0.34, n=0.5~1, MⅡFor Mg2+、Zn2+With
Cu2+One of or it is a variety of；MⅢFor from Al3+、Fe3+、Co3+One of or it is a variety of；Interlayer anion Am‐Selected from CO3 2‐、NO3 ‐、
SO4 2‐And Cl‐One of；The mass ratio of organic ceramic presoma and double-metal hydroxide containing sulfonate radical and vinyl is
1:2~1:4.
To further realize the object of the invention, it is preferable that the alkoxy silane is prestox ring tetrasilane, ethyl three
One of methoxy silane, methyltriethoxysilane and phenyl triethoxysilane are a variety of.
Preferably, the vinylsiloxane is in vinyltrimethoxysilane and vinyltriethoxysilane
It is one or more.
Preferably, the organic solvent is diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Isosorbide-5-Nitrae-dioxane, first
One of benzene and n-butanol are a variety of.
Preferably, the organic solvent and boric acid mass ratio are 5:1~10:1.
Preferably, the mass ratio of the dehydrated alcohol and double-metal hydroxide is 10:1~20:1.
Preferably, the additive amount of the catalyst is the 1%~3% of boric acid mole；It is described to be stirred at 25~45 DEG C
The time mixed is 10~30min.
A kind of duplex metal hydroxide nanometer piece of organic ceramic presoma modification, is made by above-mentioned preparation method；It should
The duplex metal hydroxide nanometer piece of organic ceramic presoma modification is to enter stratiform by organic ceramic presoma with intercalated form
Double-hydroxide interlayer is formed by Van der Waals force and ionic bond interaction；The diameter of the nanometer sheet is 0.5~2 μm.
Application of the duplex metal hydroxide nanometer piece of the organic ceramic presoma modification in silicon rubber, including such as
Lower step:
In terms of mass fraction, by the bimetallic hydrogen of 100 parts of silicon rubber rubber master batch and the modification of 1~5 part of organic ceramic presoma
Oxide nano-slice is kneaded 10~15min on opening rubber mixing machine, then be added 1~3 part of vulcanizing agent continue mixing 10~
15min is uniformly mixed；Finally vulcanize 15~25min under the conditions of 140~170 DEG C, 7~8MPa to form, 180~200 DEG C two sections
Vulcanize 4~6h, obtains having good flame-retardance can be with the silastic material of thermal stability.
Preferably, the silicon rubber rubber master batch is prepared via a method which: in terms of mass fraction, by 85~95 parts of low ethylene
Base raw rubber and 5~15 parts of high-vinyl raw rubbers are added in kneader, and point 3~5 35~40 parts of white carbon blacks of addition and 5~7 parts
Hydroxy silicon oil is kneaded 2~3h at room temperature, and 0.5~0.6 part of containing hydrogen silicone oil is added, continues 1~2h of mixing；Then 150 are warming up to
It~170 DEG C, vacuumizes after being kneaded 3~5h and continues 1~2h of mixing, rubber master batch is made；
The vulcanizing agent is one in 2,5- dimethyl -2,5- (t-butylperoxy) hexane and cumyl peroxide
Kind or two kinds.
Organic ceramic precursor (OCP) of the present invention effectively overcomes LDH tradition intercalation modifying agent (such as dodecyl sodium sulfonate
Salt, stearic acid etc.) thermal stability difference defect, and OCP produces ceramic barrier in combustion, has with LDH good
Cooperative flame retardant effect；In addition, OCP can increase the interlamellar spacing of LDH, be conducive to its dispersion in silicone rubber matrix, simultaneously
Vinyl on OCP-d-LDH can crosslink effect with silicon rubber strand, increase its compatibility with silicon rubber.Only need
Addition small amount (≤5phr) can effectively improve the flame retardant property and thermal stability of silicon rubber.
Compared with the existing technology, the invention has the following advantages that
1, intercalator of the present invention-organic ceramic presoma (OCP) effectively overcomes LDH tradition intercalation modifying
The defect of agent (such as dodecane sulfonate, stearate) thermal stability difference, and ceramic barrier is produced in combustion
Layer has good cooperative flame retardant effect with LDH.
2, the duplex metal hydroxide nanometer piece of the organic ceramic presoma modification prepared by the present invention contains end-vinyl,
It can crosslink and react with silicon rubber strand, there is good compatibility with silicon rubber；
3, the duplex metal hydroxide nanometer piece of the organic ceramic presoma modification prepared by the present invention has excellent heat
Stability and flame retardant property, need to only add a small amount of (≤5phr) can effectively improve the flame retardant property and thermal stability of silicon rubber
Energy.
Detailed description of the invention
Fig. 1 is the FTIR spectrogram of D4, ViTMS, BA and OCP in embodiment 1；
Fig. 2 is the FTIR spectrogram of OCP, LDH and OCP-d-LDH in embodiment 1；
Fig. 3 is the XRD spectra of SR/OCP-d-LDH in the SR/LDH and embodiment 3 of comparative example 2；
Fig. 4 is SR/OCP-d-LDH scanning electron microscope (SEM) figure in the SR/LDH and embodiment 3 of comparative example 2.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the embodiment of the present invention is not limited to
This.
Embodiment 1
(1) preparation of the organic ceramic presoma (OCP) containing sulfonate radical and vinyl
Using reflux cooling device, respectively by 15.548g (0.25mol) boric acid, 29.622g (0.1mol) prestox ring four
Siloxanes (D4) and 14.820g (0.1mol) vinyltrimethoxysilane ViTMS are added in three-necked flask, and 78mL bis- is added
0.442g (4.5mmol) H is finally added dropwise as solvent in glycol dimethyl ether2SO4As catalyst, 15min is stirred at 30 DEG C
It is sufficiently mixed reactant uniformly.80 DEG C of pre-polymerization 2h are then raised temperature to, 150 DEG C of reaction 2h are hereafter warming up to.After reaction will
It is cooled to room temperature.After washing, vacuum rotary steam, vacuum drying, the organic ceramic forerunner containing sulfonate radical and vinyl is obtained
Body (OCP), it is as shown in Equation 1 that OCP prepares reaction equation.
Fig. 1 is the FTIR spectrogram of D4, ViTMS and product.It will be seen from figure 1 that the characteristic absorption peak of D4 mainly has :-CH3
Asymmetric stretching vibration peak (2964cm‐1), Si-CH3Symmetrical deformation vibration peak (1261cm‐1) and Si-O-Si stretching vibration
Peak (1092cm‐1).The characteristic absorption peak of ViTMS mainly has :-CH3Asymmetric vibration peak and symmetrical stretching vibration peak
(2949cm‐1And 2843cm‐1), the stretching vibration peak (3060cm of C-H in C=C-H‐1), the stretching vibration peak (1600cm of C=C‐1) and Si-O-C symmetrical stretching vibration peak (1095cm‐1).BA is in 3217cm‐1The flexible vibration that neighbouring stronger broad peak is-OH
It is dynamic, 1400cm‐1Neighbouring broad peak belongs to the vibration absorption peak of B-O.In contrast, include substantially in the infrared spectrum of product OCP
The main feature absorption peak of D4, ViTMS and BA, and-OH the absorption peak for belonging to boric acid disappears substantially, illustrates that product OCP passes through
BA and unreacted B-OH are washed away substantially after washing.
(2) preparation of OCP-d-LDH
The MgAl-LDH (mass ratio OCP:LDH=1:3) that the OCP and 24g diameter of 8g is 0.5 μm is weighed first, is added
Dehydrated alcohol to volume is 240mL, and ultrasonic agitation 10min keeps its fully dispersed, then with magnetic agitation 12h, obtains white suspension
Liquid, 55 DEG C of reaction 3h.Vacuum rotary steam obtains the LDH nanometer sheet (OCP-d-LDH) of OCP modification after 50 DEG C of baking oven vacuum drying.
Fig. 2 is the FTIR spectrogram of OCP, LDH and OCP-d-LDH.From figure 2 it can be seen that handled by blending
OCP-d-LDH is in 1635-1369cm‐1Occur by 1600cm in OCP‐1C=C stretching vibration peak, 1400cm‐1Neighbouring B-O vibration
Move 1356cm in absorption peak and LDH‐1Neighbouring CO3 2‐Stretching vibration peak is superimposed the characteristic peak to be formed, and the change of peak type illustrates B-O
Key and CO3 2‐Between interacted.In 1000-600cm‐1Place's absorption peak is inhaled by the Si-O deformation vibration of Si-O-B in OCP
Receive what the vibration performance absorption peak of Mg-O and Al-O in peak and LDH was formed by stacking.Spectrogram proves exist centainly between LDH and OCP
Interaction.
(3) application of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification in silicon rubber flame-retardant
1) preparation of silicon rubber rubber master batch: in terms of mass fraction, by 85 parts of low vinyl raw rubbers and 15 parts of high-vinyl raw rubbers
It is added in kneader, and is added three times 35 parts of white carbon blacks and 5 parts of hydroxy silicon oils, be kneaded 2h at room temperature, 0.5 part of addition is hydrogeneous
Silicone oil continues 1~h of mixing；Then 150 DEG C are warming up to, is vacuumized after mixing 3h and continues to be kneaded 1h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: in terms of mass fraction, by 100 parts of silicon rubber rubber master batch and 1 part of OCP-d-LDH in opening
It is kneaded 15min on formula rubber mixing machine, 1 part of vulcanizing agent 2 is then added, (t-butylperoxy) hexane of 5- dimethyl -2,5- bis- continues
It is kneaded 15min, is uniformly mixed；Finally vulcanize 15min molding under the conditions of 165 DEG C, 8MPa, 190 DEG C of post vulcanization 5h are had
There is good flame-retardance can be with the silastic material of thermal stability.Various standard specimens are prepared on universal sampling machine, carry out anti-flammability
Energy and thermal stability test, the results are shown in Table 1.
Embodiment 2
(1) preparation of the organic ceramic presoma (OCP) containing sulfonate radical and vinyl
Using reflux cooling device, respectively by 15.548g (0.25mol) boric acid, three ethoxy of 17.830g (0.1mol) methyl
Base silane and 19.031g (0.1mol) vinyltriethoxysilane are added in three-necked flask, and 100mL1 is added, 4- dioxy six
0.735g (7.5mmol) H is finally added dropwise as solvent in ring2SO4As catalyst, stirring 30min at 25 DEG C fills reactant
Divide and is uniformly mixed.70 DEG C of pre-polymerization 5h are then raised temperature to, 160 DEG C of reaction 4h are hereafter warming up to.It is cooled to room after reaction
Temperature.After washing, vacuum rotary steam, vacuum drying, the organic ceramic presoma (OCP) containing sulfonate radical and vinyl is obtained.
(2) preparation of OCP-d-LDH
The MgAl-LDH (mass ratio OCP:LDH=1:3) that the OCP and 24g diameter of 8g is 1.0 μm is weighed first, is added
Dehydrated alcohol to volume is 350mL, and ultrasonic agitation 10min keeps its fully dispersed, then with magnetic agitation 12h, obtains white suspension
Liquid, 55 DEG C of reaction 4h.Vacuum rotary steam obtains the LDH nanometer sheet (OCP-d-LDH) of OCP modification after 50 DEG C of baking oven vacuum drying.
(3) application of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification in silicon rubber flame-retardant
1) preparation of silicon rubber rubber master batch: in terms of mass fraction, by 90 parts of low vinyl raw rubbers and 10 parts of high-vinyl raw rubbers
It is added in kneader, and point 4 40 parts of white carbon blacks of addition and 6 parts of hydroxy silicon oils, is kneaded 3h at room temperature, 0.6 part of addition is hydrogeneous
Silicone oil continues to be kneaded 2h；Then 160 DEG C are warming up to, is vacuumized after mixing 4h and continues to be kneaded 1.5h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: in terms of mass fraction, by 100 parts of silicon rubber rubber master batch and 3 parts of OCP-d-LDH in opening
It is kneaded 15min on formula rubber mixing machine, 3 parts of vulcanizing agents 2 are then added, (t-butylperoxy) hexane of 5- dimethyl -2,5- bis- continues
It is kneaded 10min, is uniformly mixed；Finally vulcanize 15min molding under the conditions of 170 DEG C, 7MPa, 200 DEG C of post vulcanization 4h are had
There is good flame-retardance can be with the silastic material of thermal stability.Various standard specimens are prepared on universal sampling machine, carry out anti-flammability
Energy and thermal stability test, the results are shown in Table 1.
Embodiment 3
(1) preparation of the organic ceramic presoma (OCP) containing sulfonate radical and vinyl
Using reflux cooling device, respectively by 15.548g (0.25mol) boric acid, 29.622g (0.1mol) prestox ring four
Siloxanes and 14.820g (0.1mol) vinyltrimethoxysilane are added in three-necked flask, and 155mL diethylene glycol second is added
As solvent 0.431g (2.5mmol) p-methyl benzenesulfonic acid is finally added dropwise as catalyst, stirring 10min at 45 DEG C makes in diether
Reactant is sufficiently mixed uniformly.95 DEG C of pre-polymerization 2h are then raised temperature to, 140 DEG C of reaction 5h are hereafter warming up to.After reaction by it
It is cooled to room temperature.After washing, vacuum rotary steam, vacuum drying, the organic ceramic presoma containing sulfonate radical and vinyl is obtained
(OCP)。
(2) preparation of OCP-d-LDH
The MgAl-LDH (mass ratio OCP:LDH=1:3) that the OCP and 24g diameter of 8g is 2.0 μm is weighed first, is added
Dehydrated alcohol to volume is 480mL, and ultrasonic agitation 10min keeps its fully dispersed, then with magnetic agitation 12h, obtains white suspension
Liquid, 60 DEG C of reaction 2h.Vacuum rotary steam obtains the LDH nanometer sheet (OCP-d-LDH) of OCP modification after 50 DEG C of baking oven vacuum drying.
(3) application of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification in silicon rubber flame-retardant
1) preparation of silicon rubber rubber master batch: in terms of mass fraction, 95 parts of low vinyl raw rubbers and 5 parts of high-vinyl raw rubbers are added
Enter in kneader, and point 5 40 parts of white carbon blacks of addition and 7 parts of hydroxy silicon oils, is kneaded 3h at room temperature, 0.6 part of Silicon Containing Hydrogen is added
Oil continues to be kneaded 2h；Then 170 DEG C are warming up to, is vacuumized after mixing 5h and continues to be kneaded 2h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: in terms of mass fraction, 100 parts of silicon rubber rubber master batch and 5 parts of OCP-d-LDH are being opened
It puts and is kneaded 10min on formula rubber mixing machine, 1.5 parts of vulcanizing agent cumyl peroxides are then added and continue to be kneaded 15min, mixing is equal
It is even；Finally under the conditions of 140 DEG C, 8MPa vulcanize 25min molding, 180 DEG C of post vulcanization 6h, obtain with good flame-retardance can and
The silastic material SR/OCP-d-LDH of thermal stability, what SR/OCP-d-LDH therein was indicated is silicon rubber (SR) with it is fire-retardant
Agent OCP-d-LDH composite material.Its scanning electron microscope (SEM) as shown in figure 4, XRD spectra as shown in figure 3, flame retardant property and heat are steady
It is as shown in Table 1 and Table 2 to determine the performance test results.
Embodiment 4
(1) preparation of the organic ceramic presoma (OCP) containing sulfonate radical and vinyl
Using reflux cooling device, respectively by 15.548g (0.25mol) boric acid, 29.622g (0.1mol) prestox ring four
Siloxanes and 14.820g (0.1mol) vinyltrimethoxysilane are added in three-necked flask, and 100mL diethylene glycol two is added
0.442g (4.5mmol) H is finally added dropwise as solvent in methyl ether2SO4As catalyst, stirring 15min at 30 DEG C makes reactant
It is sufficiently mixed uniformly.80 DEG C of pre-polymerization 2h are then raised temperature to, 150 DEG C of reaction 2h are hereafter warming up to.It is cooled to after reaction
Room temperature.After washing, vacuum rotary steam, vacuum drying, the organic ceramic presoma (OCP) containing sulfonate radical and vinyl is obtained.
(2) preparation of OCP-d-LDH
The ZnCo-LDH (mass ratio OCP:LDH=1:4) that the OCP and 24g diameter of 6g is 1.0 μm is weighed first, is added
Dehydrated alcohol to volume is 450mL, and ultrasonic agitation 10min keeps its fully dispersed, then with magnetic agitation 12h, obtains white suspension
Liquid, 55 DEG C of reaction 3h.Vacuum rotary steam obtains the LDH nanometer sheet (OCP-d-LDH) of OCP modification after 50 DEG C of baking oven vacuum drying.
(3) application of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification in silicon rubber flame-retardant
1) preparation of silicon rubber rubber master batch: in terms of mass fraction, 93 parts of low vinyl raw rubbers and 7 parts of high-vinyl raw rubbers are added
Enter in kneader, and point 4 40 parts of white carbon blacks of addition and 6 parts of hydroxy silicon oils, is kneaded 3h at room temperature, 0.6 part of Silicon Containing Hydrogen is added
Oil continues to be kneaded 2h；Then 160 DEG C are warming up to, is vacuumized after mixing 4h and continues to be kneaded 1.5h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: in terms of mass fraction, by 100 parts of silicon rubber rubber master batch and 5 parts of OCP-d-LDH in opening
It is kneaded 15min on formula rubber mixing machine, 3 parts of vulcanizing agents 2 are then added, (t-butylperoxy) hexane of 5- dimethyl -2,5- bis- continues
It is kneaded 15min, is uniformly mixed；Finally vulcanize 15min molding under the conditions of 165 DEG C, 8MPa, 190 DEG C of post vulcanization 5h are had
There is good flame-retardance can be with the silastic material of thermal stability.Various standard specimens are prepared on universal sampling machine, carry out anti-flammability
Energy and thermal stability test, the results are shown in Table 1.
Embodiment 5
(1) preparation of the organic ceramic presoma (OCP) containing sulfonate radical and vinyl
Using reflux cooling device, respectively by 15.548g (0.25mol) boric acid, 29.622g (0.1mol) prestox ring four
Siloxanes and 14.820g (0.1mol) vinyltrimethoxysilane are added in three-necked flask, and 100mL diethylene glycol two is added
0.442g (4.5mmol) H is finally added dropwise as solvent in methyl ether2SO4As catalyst, stirring 15min at 30 DEG C makes reactant
It is sufficiently mixed uniformly.80 DEG C of pre-polymerization 2h are then raised temperature to, 150 DEG C of reaction 2h are hereafter warming up to.It is cooled to after reaction
Room temperature.After washing, vacuum rotary steam, vacuum drying, the organic ceramic presoma (OCP) containing sulfonate radical and vinyl is obtained.
(2) preparation of OCP-d-LDH
The MgAl-LDH (mass ratio OCP:LDH=1:2) that the OCP and 20g diameter of 10g is 1.0 μm is weighed first, is added
Dehydrated alcohol to volume is 450mL, and ultrasonic agitation 10min keeps its fully dispersed, then with magnetic agitation 12h, obtains white suspension
Liquid, 55 DEG C of reaction 3h.Vacuum rotary steam obtains the LDH nanometer sheet (OCP-d-LDH) of OCP modification after 50 DEG C of baking oven vacuum drying.
(3) application of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification in silicon rubber flame-retardant
1) preparation of silicon rubber rubber master batch: in terms of mass fraction, 93 parts of low vinyl raw rubbers and 7 parts of high-vinyl raw rubbers are added
Enter in kneader, and point 4 40 parts of white carbon blacks of addition and 6 parts of hydroxy silicon oils, is kneaded 3h at room temperature, 0.6 part of Silicon Containing Hydrogen is added
Oil continues to be kneaded 2h；Then 160 DEG C are warming up to, is vacuumized after mixing 4h and continues to be kneaded 1.5h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: in terms of mass fraction, by 100 parts of silicon rubber rubber master batch and 5 parts of OCP-d-LDH in opening
It is kneaded 15min on formula rubber mixing machine, 2 parts of vulcanizing agent cumyl peroxides are then added and continue to be kneaded 15min, are uniformly mixed；Most
Vulcanize 15min molding under the conditions of 165 DEG C, 8MPa afterwards, 190 DEG C of post vulcanization 5h, obtaining can be steady with heat with good flame-retardance
The flame-proof silicon rubber of qualitative energy.Various standard specimens are prepared on universal sampling machine, carry out flame retardant property and thermal stability test, knot
Fruit is as shown in table 1.
Comparative example 1
In order to prove the flame retardant effect of OCP-d-LDH, as a comparison with pure silicone rubber (SR) sample.
1) preparation of rubber master batch: in terms of mass fraction, 93 parts of low vinyl raw rubbers and 7 parts of high-vinyl raw rubbers are added and are mediated
In machine, and point 4 40 parts of white carbon blacks of addition and 6 parts of hydroxy silicon oils, it is kneaded 3h at room temperature, 0.6 part of containing hydrogen silicone oil is added, continues
It is kneaded 2h；Then 160 DEG C are warming up to, is vacuumized after mixing 4h and continues to be kneaded 1.5h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: in terms of mass fraction, 100 parts of silicon rubber rubber master batch are kneaded on opening rubber mixing machine
2 parts of vulcanizing agents 2 are then added in 15min, and (t-butylperoxy) hexane of 5- dimethyl -2,5- bis- continues 15min, are uniformly mixed；
Finally vulcanize 15min molding under the conditions of 165 DEG C, 8MPa, 190 DEG C of post vulcanization 5h obtain pure silicone rubber sample.In omnipotent system
Various standard specimens are prepared on model machine, carry out flame retardant property and thermal stability test, as a result as shown in Table 1 and Table 2.
Comparative example 2
In order to further compare the flame retardant effect of OCP, LDH and OCP-d-LDH, LDH is used alone and is added as fire retardant
Into SR matrix.
1) preparation of silicon rubber rubber master batch: in terms of mass fraction, 93 parts of low vinyl raw rubbers and 7 parts of high-vinyl raw rubbers are added
Enter in kneader, and point 4 40 parts of white carbon blacks of addition and 6 parts of hydroxy silicon oils, is kneaded 3h at room temperature, 0.6 part of Silicon Containing Hydrogen is added
Oil continues to be kneaded 2h；Then 160 DEG C are warming up to, is vacuumized after mixing 4h and continues to be kneaded 1.5h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: being 1.0 μm by 100 parts of silicon rubber rubber master batch and 5 parts of diameters in terms of mass fraction
LDH is kneaded 15min on opening rubber mixing machine, and 1.5 parts of vulcanizing agents 2, bis- (t-butyl peroxy of 5- dimethyl -2,5- is then added
Base) hexane continuation 15min, it is uniformly mixed；Finally vulcanize 15min molding, 190 DEG C of post vulcanizations under the conditions of 165 DEG C, 8MPa
5h, obtains SR/LDH sample, and SEM schemes as shown in figure 4, XRD spectra is as shown in Figure 4.Various marks are prepared on universal sampling machine
Sample carries out flame retardant property and thermal stability test, as a result as shown in Table 1 and Table 2.
Comparative example 3
In order to further compare the flame retardant effect of OCP, LDH and OCP-d-LDH, OCP is used alone and is added as fire retardant
Into SR matrix.
1) preparation of silicon rubber rubber master batch: in terms of mass fraction, 93 parts of low vinyl raw rubbers and 7 parts of high-vinyl raw rubbers are added
Enter in kneader, and point 4 40 parts of white carbon blacks of addition and 6 parts of hydroxy silicon oils, is kneaded 3h at room temperature, 0.6 part of Silicon Containing Hydrogen is added
Oil continues to be kneaded 2h；Then 160 DEG C are warming up to, is vacuumized after mixing 4h and continues to be kneaded 1.5h, rubber master batch is made；
2) preparation of flame-proof silicon rubber: in terms of mass fraction, by 100 parts of silicon rubber rubber master batch and 5 parts of OCP in open refining glue
It is kneaded 15min on machine, 1.5 parts of vulcanizing agents 2 are then added, (t-butylperoxy) hexane of 5- dimethyl -2,5- bis- continues
15min is uniformly mixed；Finally vulcanize 15min molding under the conditions of 165 DEG C, 8MPa, 190 DEG C of post vulcanization 5h obtain SR/OCP
Sample.Various standard specimens are prepared on universal sampling machine, flame retardant property and thermal stability test are carried out, as a result such as Tables 1 and 2 institute
Show.
Test method
1, Fourier transform infrared spectroscopy (FTIR): sample is mixed and tabletted with potassium bromide powder, use is infrared
Interference light penetrates sample and collects the interference signal of sample.Wave-number range is 4000-400cm-1, precision 4cm-1。
2, scanning electron microscope analysis (SEM): sample is adhered on sample stage by conducting resinl, and is carried out at the metal spraying of surface
Reason.It is the electron beam scanning imagery of 5kV with acceleration voltage, observes the pattern of sample surfaces.
3, X-ray diffraction analysis (XRD): sample dispersion in solvent and is applied on monocrystalline silicon piece, and natural drying allows molten
Agent volatilization.Use Cu-K alpha ray with the rate scanning sample of 4 °/min, acceleration voltage and accelerate electric current be respectively 40kV and
20mA collects the diffraction information that 2 angle θ of sample is 1-80 °.
4, thermogravimetric analysis (TGA): in air atmosphere, taking 5mg~10mg sample to be tested in thermogravimetric analyzer, point
Eutectoid temperature range is 30-800 DEG C, and heating rate is 20 DEG C/min.
5, flame retardant property is tested: limit oxygen index (LOI) executes test according to ASTM D2863 standard, and specimen size is
120mm×6.5mm×3mm；Taper calorimetric (CCT) executes test, specimen size 100mm according to standard ISO 5660-1 standard
×100mm×4mm。
Fig. 3 is the XRD spectra of the SR/LDH of comparative example 2 and the SR/OCP-d-LDH of embodiment 3, it can be seen from the figure that
There is apparent diffraction maximum at 11.63 ° and 23.4 ° in SR/LDH, respectively corresponds (003) and (006) crystal face of LDH crystal.And
In the XRD spectra of SR/OCP-d-LDH, (003) and (006) diffraction maximum of LDH, which dies down, to broaden, this is because OCP increases LDH
Interlamellar spacing, be conducive to silicon rubber strand intercalation and enter LDH interlayer, LDH is made to be dispersed in silicon rubber in the form of intercalation or removing
In matrix body.It may also confirm that from SEM photograph (Fig. 4), dispersibility of the LDH after OCP is modified in SR is obviously improved.
Table 1
From 1 Comparative Examples 1 and 2 of table and 3 as can be seen that individually addition LDH or OCP can improve silicon rubber to a certain extent
Thermal stability and flame retardant property.And after adding OCP-d-LDH, LOI value, temperature of initial decomposition and the maximum heat of silicon rubber
Decomposition rate temperature is significantly improved.Meanwhile from embodiment 1,2 and 3 it can be seen that with OCP-d-LDH additive amount
5phr is increased to by 1phr, the LOI value of silicon rubber and 800 DEG C of carbon lefts gradually increase, and thermal stability also gradually increases.It needs
Illustrate, the additive amount of fire retardant is respectively 1 part, 3 parts and 5 parts in embodiment 1,2 and 3, and in comparative example 2 and 3, OCP and
The additive amount of LDH is 5 parts, thus for comparative example, the thermal stability of Examples 1 and 2 is slightly worse, but although fire retardant
The additive amount embodiment of the present invention 1 and 2 differs larger with comparative example 2 and 3, but thermal stability is substantially suitable, in the number phase of addition
(embodiment 3 and comparative example 2,3) simultaneously, the thermal stability of OCP-d-LDH is significantly improved.
Table 2
From 2 comparative example 1 of table it is found that SR can release a large amount of heat in combustion, heat is reached after lighting 110s and is released
Put rate peak value (PHRR), up to 257.1kW/m2.When Comparative Examples 1 and 2 and 3 explanations are individually added into OCP and LDH of 5wt%, SR
PHRR, AV-HRR and THR there is a degree of reduction, this illustrates that OCP and LDH all have certain flame retardant property, can be with
Reduce heat release when silicon rubber burning.When adding OCP-d-LDH (embodiment 3) of 5wt%, silicon rubber is surveyed in taper calorimetric
Flame retardant property outstanding is shown in examination, PHRR, AV-HRR and THR of silicon rubber reduce 54.4%, 45.5% compared with SR respectively
With 44.9%.Probably due to: one side OCP promotes dispersion of the LDH in SR, so that LDH has preferably played lamella barrier
Effect；On the other hand, OCP produces ceramic barrier, the biography of effective trap heat, oxygen and fuel gas in combustion
It is defeated, it plays a protective role to polymeric matrix.It can be seen that there is synergistic effect between OCP of the present invention and LDH, OCP is promoted
The dispersion of LDH, while while burning, generates ceramic barrier, plays fire retardation jointly with LDH.
The present invention is not constrained by above-described embodiment, and others are any to be made without departing from the spirit and principles of the present invention
Changes, modifications, substitutions, combinations, simplifications, should be equivalent alternative, be included within the scope of the present invention.
Claims (10)
1. the preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification, it is characterised in that including following step
It is rapid:
(1) preparation of the organic ceramic presoma containing sulfonate radical and vinyl
Boric acid, alkoxy silane and vinylsiloxane are added in reaction kettle, and organic solvent and catalyst is added, 25~
It is stirred at 45 DEG C, is sufficiently mixed reactant uniformly；70~95 DEG C of 2~5h of pre-polymerization are warming up to, then are warming up to 140~160 DEG C instead
Answer 2~5h；It is cooled to room temperature after reaction；After washing, vacuum rotary steam, vacuum drying, obtain containing sulfonate radical and ethylene
The organic ceramic presoma of base；Controlling boron atom and the control of silicon atom molar ratio is B:Si=1:4~1:7；Alkoxy silane with
Vinyl silanes molar ratio is 1:1~3:1；The catalyst is one or both of sulfuric acid and p-methyl benzenesulfonic acid；
(2) preparation of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification
Organic ceramic presoma, double-metal hydroxide and dehydrated alcohol containing sulfonate radical and vinyl are mixed, ultrasound is stirred
Mixing keeps its fully dispersed, then with magnetic agitation, obtains white suspension；55~60 DEG C of 2~4h of reaction, vacuum rotary steam, vacuum are dry
The duplex metal hydroxide nanometer piece of organic ceramic presoma modification is obtained after dry；Its general structure of the double-metal hydroxide
Are as follows: [MⅡ 1‐xMⅢ x(OH)2]x+(Am‐)x/m·nH2O, wherein x=0.17~0.34, n=0.5~1, MⅡFor Mg2+、Zn2+And Cu2+
One of or it is a variety of；MⅢFor from Al3+、Fe3+、Co3+One of or it is a variety of；Interlayer anion Am‐Selected from CO3 2‐、NO3 ‐、
SO4 2‐And Cl‐One of；The mass ratio of organic ceramic presoma and double-metal hydroxide containing sulfonate radical and vinyl is
1:2~1:4.
2. the preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification according to claim 1,
It is characterized in that, the alkoxy silane is prestox ring tetrasilane, ethyl trimethoxy silane, methyltriethoxysilane
With one of phenyl triethoxysilane or a variety of.
3. the preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification according to claim 1,
It is characterized in that, the vinylsiloxane is one of vinyltrimethoxysilane and vinyltriethoxysilane
Or it is a variety of.
4. the preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification according to claim 1,
It is characterized in that, the organic solvent be diethylene glycol diethyl ether, diethylene glycol dimethyl ether, Isosorbide-5-Nitrae-dioxane, toluene and
One of n-butanol is a variety of.
5. the preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification according to claim 1,
It is characterized in that, the organic solvent and boric acid mass ratio are 5:1~10:1.
6. the preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification according to claim 1,
It is characterized in that, the mass ratio of the dehydrated alcohol and double-metal hydroxide is 10:1~20:1.
7. the preparation method of the duplex metal hydroxide nanometer piece of organic ceramic presoma modification according to claim 1,
It is characterized in that, the additive amount of the catalyst is the 1%~3% of boric acid mole；It is described to stir at 25~45 DEG C
Time is 10~30min.
8. a kind of duplex metal hydroxide nanometer piece of organic ceramic presoma modification, it is characterised in that it is by claim 1-7
Described in any item preparation methods are made；The duplex metal hydroxide nanometer piece of organic ceramic presoma modification is by organic pottery
Porcelain presoma enters layered double-hydroxide interlayer with intercalated form, is formed by Van der Waals force and ionic bond interaction；
The diameter of the nanometer sheet is 0.5~2 μm.
9. duplex metal hydroxide nanometer piece the answering in silicon rubber of organic ceramic presoma modification according to any one of claims 8
With, it is characterised in that include the following steps:
In terms of mass fraction, by the bimetal hydroxide of 100 parts of silicon rubber rubber master batch and the modification of 1~5 part of organic ceramic presoma
Object nanometer sheet is kneaded 10~15min on opening rubber mixing machine, and 1~3 part of vulcanizing agent is then added and continues 10~15min of mixing,
It is uniformly mixed；Finally vulcanize 15~25min molding, 180~200 DEG C of post vulcanizations 4 under the conditions of 140~170 DEG C, 7~8MPa
~6h obtains having good flame-retardance can be with the silastic material of thermal stability.
10. the duplex metal hydroxide nanometer piece of organic ceramic presoma modification according to claim 9 is in silicon rubber
Application, which is characterized in that the silicon rubber rubber master batch is prepared via a method which: low by 85~95 parts in terms of mass fraction
Vinyl raw rubber and 5~15 parts of high-vinyl raw rubbers are added in kneaders, and point 3~5 35~40 parts of white carbon blacks of addition and 5~
7 parts of hydroxy silicon oils are kneaded 2~3h at room temperature, and 0.5~0.6 part of containing hydrogen silicone oil is added, continues 1~2h of mixing；Then it is warming up to
It 150~170 DEG C, vacuumizes after being kneaded 3~5h and continues 1~2h of mixing, rubber master batch is made；
The vulcanizing agent be 2,5- dimethyl -2,5- (t-butylperoxy) one of hexane and cumyl peroxide or
Two kinds.
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