CN117126462A - Graphene oxide/organic silicon/melamine hybrid flame-retardant epoxy resin and application thereof - Google Patents
Graphene oxide/organic silicon/melamine hybrid flame-retardant epoxy resin and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 66
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 66
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 35
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title abstract description 12
- 229910052710 silicon Inorganic materials 0.000 title abstract description 12
- GODPFUMSYGXUGH-UHFFFAOYSA-N silicon;1,3,5-triazine-2,4,6-triamine Chemical compound [Si].NC1=NC(N)=NC(N)=N1 GODPFUMSYGXUGH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 36
- -1 hydroxyl modified melamine Chemical class 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002210 silicon-based material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006482 condensation reaction Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001299 aldehydes Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000005375 organosiloxane group Chemical group 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 150000007974 melamines Chemical class 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 150000002192 fatty aldehydes Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- ZWTJVXCCMKLQKS-UHFFFAOYSA-N diethoxy(ethyl)silicon Chemical compound CCO[Si](CC)OCC ZWTJVXCCMKLQKS-UHFFFAOYSA-N 0.000 claims description 2
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical class [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- JXUKBNICSRJFAP-LBPRGKRZSA-N triethoxy-[3-[[(2r)-oxiran-2-yl]methoxy]propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOC[C@H]1CO1 JXUKBNICSRJFAP-LBPRGKRZSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 230000002195 synergetic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009396 hybridization Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 239000004593 Epoxy Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
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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 graphene oxide/organic silicon/melamine hybrid flame-retardant epoxy resin and application thereof, wherein the flame-retardant epoxy resin is prepared by reacting hydroxyl modified melamine, organic siloxane and modified graphene oxide; the modified graphene oxide is obtained by modifying graphene oxide by aminosilicone. According to the graphene oxide-organic silicon-melamine hybrid, hydroxyl modified melamine, organic siloxane and modified graphene oxide are subjected to a hybridization reaction to form the flame retardant of the ternary hybridization system. The layered structure and physical barrier effect of the modified graphene oxide reduce the flammability of the epoxy resin and prevent energy transfer; and a synergistic flame-retardant system is formed with the melamine compound with the chain-type structure organic silicon and nitrogen heterocyclic structure, so that the flame-retardant epoxy resin composite material can be prepared, and the flame retardance and mechanical property of the material are effectively improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to graphene oxide/organic silicon/melamine hybrid flame-retardant epoxy resin and application thereof.
Background
Epoxy resins have the advantages of excellent thermal properties, mechanical properties, chemical resistance, dimensional stability and the like, and are widely used in many fields. The oxygen index of the pure epoxy resin is only about 20%, and the pure epoxy resin is extremely easy to burn, so that the application of the pure epoxy resin is greatly limited, and the improvement of the flame retardant property of the pure epoxy resin is one of hot spots of current researches. The flame retardant used for resin materials such as epoxy resin is mainly halogen flame retardant and halogen-free flame retardant. And the halogen-containing flame-retardant material can generate a large amount of smoke and toxic corrosive hydrogen halide gas in the flame-retardant process, so that secondary hazard is caused. The halogen-free flame retardant is the main stream of the flame retardant material market, and mainly comprises flame retardant systems such as metal hydroxide flame retardant, organic phosphorus flame retardant, organic nitrogen flame retardant, silicon flame retardant and the like. Research shows that the mixed use of two or more flame retardants can achieve synergistic flame retardant effect, such as phosphorus flame retardants and nitrogen flame retardants, and the mixed use of phosphorus flame retardants and silicon flame retardants has synergistic flame retardant effect, so that the flame retardance of the material is greatly improved; however, the mechanical strength of the material is easily affected by the mixing of the two flame retardants due to poor compatibility between the materials.
Graphene is a material composed of carbon atoms and sp 2 The hybridized orbit forms a hexagonal two-dimensional carbon nanomaterial with honeycomb lattice. The composite coating has large specific surface area, specific layered structure, high mechanical strength and good thermal stability, so that the composite coating becomes an effective reinforcing filler for preparing the composite coating; the graphene oxide has a unique lamellar structure like graphene, has reactive functional groups, and has great prospect in the application of improving the barrier property, mechanical property and flame retardance of materials. Yuan Gao (2018) and the like synthesize a novel graphene-organophosphorus-organosilicon ternary grafted flame retardant and research the application of the novel graphene-organophosphorus-organosilicon ternary grafted flame retardant in polypropylene. However, there is no report on improvement of mechanical property and flame retardance of the epoxy resin material based on graphene preparation.
Disclosure of Invention
Based on the above, the invention provides the graphene oxide-organic silicon-melamine hybrid, which can enable the epoxy resin material to have excellent flame retardant property and mechanical property.
In a first aspect, the invention provides a graphene oxide-organic silicon-melamine hybrid, which is characterized by being prepared by reacting hydroxyl modified melamine, a silicon-containing compound and modified graphene oxide; the hydroxyl modified melamine is prepared by reacting melamine with short-chain aldehyde, the modified graphene oxide is prepared by modifying graphene oxide by silane or siloxane with active groups, the active groups are used for condensation reaction with the hydroxyl of the hydroxyl modified melamine, and the silicon-containing compound comprises organosiloxane and/or silica sol.
In a second aspect, the invention provides a preparation method of graphene oxide-organic silicon-melamine hybrid, which comprises the following steps:
and uniformly mixing hydroxyl modified melamine, a silicon-containing compound and modified graphene oxide, adding a catalyst, and performing hydrolytic condensation reaction for 3-8 hours at the temperature of 30-60 ℃ to obtain the ternary graphene oxide-organic silicon-melamine hybrid.
The synthetic route is as follows:
the third aspect of the invention provides a flame-retardant epoxy resin composite material prepared from epoxy resin, graphene oxide-organic silicon-melamine hybrid, a curing agent and a curing catalyst.
The fourth aspect of the invention provides a preparation method of a flame-retardant epoxy resin composite material, which comprises the following steps:
adding graphene oxide-organic silicon-melamine hybrid into epoxy resin, stirring uniformly at room temperature, adding a curing agent and a curing catalyst, curing for 0.5-1.5h at 140-160 ℃, and then curing for 3-5h at 190-210 ℃ to obtain the flame-retardant epoxy resin composite material.
According to the graphene oxide-organic silicon-melamine hybrid, hydroxyl modified melamine, silicon-containing compounds and modified graphene oxide are subjected to a hybridization reaction to form a flame retardant of a hybridization system. The layered structure and physical barrier effect of the modified graphene oxide in the graphene oxide-organic silicon-melamine hybrid reduce the flammability of the epoxy resin and prevent energy transfer; and a synergistic flame-retardant system is formed with the melamine with the chain-type structure organic silicon and nitrogen heterocyclic structure, so that the flame-retardant epoxy resin composite material can be prepared, and the flame retardance and mechanical property of the material are effectively improved.
The modified graphene oxide is obtained by modifying graphene oxide by adopting aminosilicone, the modified graphene oxide has good compatibility with an epoxy resin system or an organic flame retardant after the siloxane is modified on the surface of the modified graphene oxide, the surface of the modified graphene oxide is rich in carboxyl, amino and silicon hydroxyl, and the modified graphene oxide can be subjected to condensation reaction with the hydroxyl on hydroxyl modified melamine and the silicon hydroxyl of the organosiloxane under the catalytic action to form a synergistic flame retardant system, so that the flame retardant effect is greatly enhanced. Meanwhile, the graphene oxide-organic silicon-melamine hybrid has good dispersion performance in an epoxy resin system, the graphene oxide-organic silicon-melamine hybrid contains silicon hydroxyl, hydroxyl and carboxyl which can participate in the curing reaction of the epoxy resin, and the obtained composite material has excellent flame retardant property and mechanical property, and the limiting oxygen index LOI is 23-31; the flame retardant property can reach UL94V-0 level.
Detailed Description
The technical scheme of the invention is further described by the following specific examples. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
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 invention provides a graphene oxide-organic silicon-melamine hybrid which is prepared by reacting hydroxyl modified melamine, a silicon-containing compound and modified graphene oxide; the hydroxyl modified melamine is prepared by reacting melamine with short-chain aldehyde, the modified graphene oxide is prepared by modifying graphene oxide by silane or siloxane with active groups, the active groups are used for condensation reaction with the hydroxyl of the hydroxyl modified melamine, and the silicon-containing compound comprises organosiloxane and/or silica sol.
In some of these embodiments, the silane or siloxane having a reactive group is selected from the group consisting of epoxysilanes, aminosilicones, and isocyanatosilanes.
In some of these embodiments, the organosiloxane is selected from one or a combination of two or more of methyltriethoxysilane, methyltrimethoxysilane, methyldiethoxysilane, polymethyltriethoxysilane oligomer (mn=600-1000 g/mol), polymethyltrimethoxysilane oligomer (mn=600-1000 g/mol), ethyldiethoxysilane, r-aminopropyl triethoxysilane, r-glycidoxypropyl triethoxysilane, glycidoxypropyl trimethoxysilane, r-isocyanatopropyl triethoxysilane, or silica sol.
In some of these embodiments, the short chain aldehyde is a C1-C6 fatty aldehyde, preferably a C1-C3 fatty aldehyde, more preferably formaldehyde.
In some of these embodiments, the structure of the graphene oxide-silicone-melamine hybrid is as follows:
in some of these embodiments, the modified graphene oxide has the structural formula:
in some of these embodiments, the structure of the hydroxy-modified melamine is as follows;
in some of these embodiments, the mass ratio of hydroxyl modified melamine, silicon containing compound, and modified graphene oxide is (10-50): (20-50): (1-5).
In some of these embodiments, the melamine and short chain aldehyde are present in a mass ratio of (5-15): (10-30).
In some of these embodiments, the aminosilicone and graphene oxide are in a mass ratio of (10-50): (0.5-5).
In some of these embodiments, the hydroxy-modified melamine is prepared by a process comprising: mixing melamine and formaldehyde, regulating the pH value to 8-9, and reacting at 60-90 ℃ for 0.5-2h to obtain the hydroxyl modified melamine.
In some embodiments, the preparation method of the modified graphene oxide comprises the following steps: adding ethanol solvent into graphene oxide, performing ultrasonic dispersion for 0.5-1h at 30-50 ℃, then dropwise adding aminosilicone, and performing stirring reflux reaction for 3-5h at 60-100 ℃ to obtain the modified graphene oxide.
The preparation method of the graphene oxide-organic silicon-melamine hybrid comprises the following steps:
and uniformly mixing hydroxyl modified melamine, a silicon-containing compound and modified graphene oxide, adding a catalyst, and performing hydrolytic condensation reaction at 30-60 ℃ for 3-8 hours to obtain the graphene oxide-organic silicon-melamine hybrid.
The synthetic route is as follows:
in some of these embodiments, the catalyst for the hydrolytic condensation reaction is selected from dibutyl tin dilaurate or triethylamine.
In some of these embodiments, the mass ratio of the catalyst to the modified graphene oxide is (0.3-1.2): (1-5).
A flame-retardant epoxy resin composite material is prepared from epoxy resin, graphene oxide-organic silicon-melamine hybrid, a curing agent and a curing catalyst.
In some of these embodiments, the mass ratio of the epoxy resin to graphene oxide-silicone-melamine hybrid is (90-110): (5-30), preferably 100: (5-30), more preferably 100: (10-25).
In some embodiments, the curing agent contains hydroxyl bonds or nitrogen hydrogen bonds, and the equivalent ratio of the hydroxyl bonds or nitrogen hydrogen bonds of the curing agent to the epoxy groups of the epoxy resin is 1: (0.8-1.2).
In some embodiments, the curing agent is selected from one or a combination of two or more of novolac epoxy resins, bisphenol a novolac epoxy resins, or 4,4' -diaminodiphenylmethane.
In some of these embodiments, the curing catalyst is selected from the group consisting of triethylamine, 2-methyl-4-ethylimidazole, 2-ethylimidazole, and 2-methylimidazole.
In some of these embodiments, the mass ratio of the curing catalyst to the epoxy resin is (0.1-2): 100.
the preparation method of the flame-retardant epoxy resin composite material comprises the following steps:
adding graphene oxide-organic silicon-melamine hybrid into epoxy resin, stirring uniformly at room temperature, adding a curing agent and a curing catalyst, curing for 0.5-1.5h at 140-160 ℃, and then curing for 3-5h at 190-210 ℃ to obtain the flame-retardant epoxy resin composite material.
The following are specific examples.
Example 1
The preparation method of the graphene oxide-organic silicon-melamine hybrid comprises the following steps:
(1) Adding 3g of graphene oxide (average radial dimension: 30-40 um) into 1000mL of ethanol solvent, and performing ultrasonic dispersion at 30-50 ℃ for 0.5-1 hour; then, 30g of gamma-aminopropyl triethoxysilane is added dropwise, and reflux reaction is carried out for 4 hours at the temperature of 80 ℃ under mechanical stirring; filtering, washing for 4 times sequentially by using ethanol and acetone, and drying in a 90 ℃ oven for 7 hours to obtain amino-functionalized modified graphene oxide;
(2) Adding 10g of melamine and 20g of formaldehyde solution into a reaction vessel, adjusting the pH to be 8.5, and reacting for 1h at 75 ℃ to obtain hydroxyl modified melamine;
the structure of the hydroxyl modified melamine is shown as a formula I;
(3) 3g of modified graphene oxide, 10g of polymethyl triethoxy siloxane oligomer, 10g of dimethyl diethoxy silane and 10g of glycidoxypropyl trimethoxy silane are added into 30g of hydroxyl modified melamine, and hydrolysis condensation reaction is carried out for 5 hours at 45 ℃ under the action of 0.5g of catalyst dibutyl tin dilaurate, so that graphene oxide-organic silicon-melamine hybrid is obtained.
The synthetic route is as follows:
example 2
The preparation method of the graphene oxide-organic silicon-melamine hybrid comprises the following steps:
(1) 0.5g of graphene oxide (average radial dimension: 20-30 um) was added to 1000mL of ethanol solvent, and dispersed ultrasonically at 30℃for 0.5 hours; then, 10g of gamma-glycidoxypropyl triethoxysilane is added dropwise, and reflux reaction is carried out for 3 hours at the temperature of 60 ℃ under mechanical stirring; filtering, sequentially washing 3 times with ethanol and acetone, and drying in an oven at 80 ℃ for 5 hours to obtain modified graphene oxide;
(2) Adding 5g of melamine and 10g of formaldehyde solution into a reaction vessel, adjusting pH to be 8, and reacting at 60 ℃ for 0.5h to obtain hydroxyl modified melamine;
(3) Adding 1g of modified graphene oxide, 5g r-isocyanatopropyl triethoxysilane, 5g of silica sol and 10g of methyldiethoxysilane into 10g of hydroxyl modified melamine, and carrying out hydrolytic condensation reaction for 3 hours at 30 ℃ under the action of 0.1g of catalyst triethylamine to obtain the graphene oxide-organic silicon-melamine hybrid.
Example 3
The preparation method of the graphene oxide-organic silicon-melamine hybrid comprises the following steps:
(1) Adding 5g of graphene oxide (average radial dimension: 30-40 um) into 1000mL of ethanol solvent, and performing ultrasonic dispersion at 50 ℃ for 1 hour; then, dropwise adding 10g r-isocyanatopropyl triethoxysilane, and carrying out reflux reaction for 5 hours at the temperature of 100 ℃ under mechanical stirring; filtering, sequentially washing with ethanol and acetone for 5 times, and drying in a 100 ℃ oven for 10 hours to obtain modified graphene oxide;
(2) Adding 15g of melamine and 30g of formaldehyde solution into a reaction vessel, adjusting the pH to be 9, and reacting for 2 hours at 90 ℃ to obtain hydroxyl modified melamine;
(3) 5g of modified graphene oxide, 10g of methyltriethoxysilane, 10g of methyltrimethoxysilane and 30g of methyldiethoxysilane are added into 50g of hydroxyl modified melamine, and hydrolysis condensation reaction is carried out for 8 hours at 60 ℃ under the action of 0.1g of catalyst triethylamine, so that graphene oxide-organic silicon-melamine hybrid is obtained.
Example 4
A preparation method of a flame-retardant epoxy resin composite material comprises the following steps:
and adding 5g of the ternary graphene oxide-organic silicon-melamine hybrid obtained in the embodiment 1 into 100g of epoxy resin, uniformly stirring at room temperature, adding a proper amount of phenolic resin curing agent and 1g of catalyst triethylamine, wherein the hydroxyl equivalent ratio of the epoxy equivalent to the curing agent is 1:1, curing at 150 ℃ for 1h, and then curing at 200 ℃ for 4h to obtain the graphene oxide-organic silicon-melamine hybrid composite epoxy flame-retardant material.
Example 5
A preparation method of a flame-retardant epoxy resin composite material comprises the following steps:
adding 10g of graphene oxide-organic silicon-melamine hybrid obtained in the embodiment 2 into 100g of epoxy resin, uniformly stirring at room temperature, adding a proper amount of phenolic epoxy resin curing agent and a catalyst of 0.6g of 2-ethylimidazole, wherein the ratio of epoxy group equivalent of the epoxy resin to hydroxyl equivalent of the curing agent is 1:1, curing for 1h at 150 ℃, and then curing for 4h at 200 ℃ to obtain the graphene oxide-organic silicon-melamine hybrid composite epoxy flame-retardant material.
Example 6
A preparation method of a flame-retardant epoxy resin composite material comprises the following steps:
adding 10g of graphene oxide-organic silicon-melamine hybrid obtained in the example 3 and 5g of the graphene oxide-organic silicon-melamine hybrid obtained in the example 1 into 100g of epoxy resin, uniformly stirring at room temperature, adding a proper amount of bisphenol A phenolic resin curing agent and a catalyst of 0.5g of 2-methyl-4-ethylimidazole, wherein the ratio of epoxy equivalent to hydroxyl equivalent of the curing agent is 1:1, curing for 1h at 150 ℃, and then curing for 4h at 200 ℃ to obtain the graphene oxide-organic silicon-melamine hybrid composite epoxy flame-retardant material.
Example 7
A preparation method of a flame-retardant epoxy resin composite material comprises the following steps:
and adding 15g of graphene oxide-organic silicon-melamine hybrid obtained in the example 1 and 20g of the graphene oxide-organic silicon-melamine hybrid obtained in the example 2 into 100g of epoxy resin, uniformly stirring at room temperature, adding a proper amount of bisphenol A phenolic resin curing agent and a curing catalyst, namely 2-methylimidazole, and curing for 4 hours at 150 ℃ after the epoxy equivalent ratio of epoxy equivalent to curing agent is 1:1, so as to obtain the graphene oxide-organic silicon-melamine hybrid composite epoxy flame-retardant material.
Example 8
A preparation method of a flame-retardant epoxy resin composite material comprises the following steps:
adding 30g of graphene oxide-organic silicon-melamine hybrid obtained in example 3 into 100g of epoxy resin, stirring uniformly at room temperature, adding a proper amount of 4,4' -diaminodiphenylmethane curing agent and catalyst 2-ethylimidazole in an amount of 0.2g, wherein the equivalent ratio of epoxy groups of the epoxy resin to N-H of the curing agent is 1:1, curing for 1H at 150 ℃, and then curing for 4H at 200 ℃ to obtain the graphene oxide-organic silicon-melamine hybrid composite epoxy flame-retardant material.
Comparative example 1
The preparation method of the epoxy resin composite material comprises the following steps:
taking 100g of epoxy resin, adding a proper amount of 4, 4-diaminodiphenyl methane curing agent and 1g of catalyst triethylamine, wherein the N-H equivalent ratio of the epoxy equivalent to the curing agent is 1:1, curing for 1H at 150 ℃, and then curing for 4H at 200 ℃ to obtain the epoxy resin composite epoxy flame-retardant material.
Comparative example 2
A preparation method of a flame-retardant epoxy resin composite material comprises the following steps:
adding 5g of organosilicon-melamine hybrid into 100g of epoxy resin, stirring uniformly at room temperature, adding a proper amount of phenolic resin curing agent and 1g of catalyst triethylamine, and curing for 1h at 150 ℃ and then for 4h at 200 ℃ according to the epoxy equivalent and the hydroxyl equivalent of the curing agent to obtain the organosilicon-melamine hybrid composite epoxy flame-retardant material.
Wherein the silicone-melamine hybrid differs from the graphene oxide-silicone-melamine hybrid of example 1 in that modified graphene oxide is not added during the preparation of the silicone-melamine hybrid.
Comparative example 3
A preparation method of a flame-retardant epoxy resin composite material comprises the following steps:
adding 5g of graphene oxide-organic silicon hybrid into 100g of epoxy resin, uniformly stirring at room temperature, adding a proper amount of phenolic resin curing agent and 1g of catalyst triethylamine, and curing for 1h at 150 ℃ and then for 4h at 200 ℃ according to the epoxy equivalent and the hydroxyl equivalent of the curing agent to obtain the graphene oxide-melamine hybrid composite epoxy flame-retardant material.
The graphene oxide-organosilicon hybrid is different from the graphene oxide-organosilicon-melamine hybrid in embodiment 1 in that hydroxyl modified melamine is not added in the preparation process of the graphene oxide-organosilicon hybrid.
Performance testing
The epoxy resin composites of examples 4-8 and comparative examples 1-3 were subjected to performance flame retardant property and mechanical property tests, wherein the combustion behavior was measured in part 2 by oxygen index method for plastics using GB/T2406.2-2009: room temperature test, oxygen index test; a vertical combustion test method in GB/T2408-2008 horizontal method and vertical method for measuring the combustion performance of plastics is adopted to carry out a vertical combustion test; impact strength is tested in a CHARPYXCJ-50 simply supported beam according to GB 1043-93 standard; the results are shown in Table 1.
TABLE 1
Referring to Table 1, it can be seen from examples 4 to 8 that the flame retardant performance of the flame retardant epoxy resin composite material of the present invention can reach UL94V-0 level, the limiting oxygen index LOI is 23.2-31.3, the impact strength is 11.4-18.2, and simultaneously, the limiting oxygen index LOI of the composite material is gradually increased and the impact strength is reduced with the increase of the content of graphene oxide-organic silicon-melamine hybrid. Wherein the mass ratio of the epoxy resin to the graphene oxide-silicone-melamine hybrid in example 6 is 100:15, the flame retardant property is obviously improved, and the mechanical property is only slightly reduced.
In the comparative example 4 and the comparative example 1, the limiting oxygen index LOI, the flame retardant property and the impact strength of the example 4 are all obviously improved compared with the epoxy resin material without the graphene oxide-organic silicon-melamine hybrid in the comparative example 1. Comparative example 4 and comparative example 2, in which a silicone-melamine hybrid was used, showed a decrease in limiting oxygen index LOI; the graphene oxide-silicone hybrid of comparative example 3 has significantly reduced limiting oxygen index LOI and impact strength compared to example 4. Experiments show that the graphene oxide-organic silicon-melamine hybrid disclosed by the invention is matched with each component to form a synergistic flame-retardant system, so that the synergistic flame-retardant system is used for preparing a flame-retardant epoxy resin composite material, and the flame retardance and mechanical property of the material can be effectively improved.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The graphene oxide-organic silicon-melamine hybrid is characterized by being prepared by reacting hydroxyl modified melamine, a silicon-containing compound and modified graphene oxide; the hydroxyl modified melamine is prepared by reacting melamine with short-chain aldehyde, the modified graphene oxide is prepared by modifying graphene oxide by silane or siloxane with active groups, the active groups are used for condensation reaction with the hydroxyl of the hydroxyl modified melamine, and the silicon-containing compound comprises organosiloxane and/or silica sol.
2. The graphene oxide-silicone-melamine hybrid according to claim 1, wherein the silane or siloxane having a reactive group is selected from the group consisting of epoxysilanes, aminosilicones, and isocyanatosilanes; the aminosilicone is selected from gamma-aminopropyl triethoxysilane; and/or the organosiloxane is selected from one or more than two of methyltriethoxysilane, methyltrimethoxysilane, methyldiethoxysilane, polymethyltriethoxysilane oligomer, polymethyltrimethoxysilane oligomer, ethyldiethoxysilane, r-aminopropyl triethoxysilane, r-glycidoxypropyl triethoxysilane and r-isocyanatopropyl triethoxysilane; and/or the number of the groups of groups,
the short chain aldehyde is a C1-C6 fatty aldehyde, preferably a C1-C3 fatty aldehyde, more preferably formaldehyde.
3. The graphene oxide-silicone-melamine hybrid according to claim 1 or 2, wherein the hydroxy-modified melamine has the structure shown in formula i;
4. the graphene oxide-silicone-melamine hybrid according to claim 1 or 2, wherein the mass ratio of the hydroxyl-modified melamine, silicon-containing compound and modified graphene oxide is (10-50): (20-50): (1-5); and/or the number of the groups of groups,
the mass ratio of the melamine to the short-chain aldehyde is (5-15): (10-30); and/or the number of the groups of groups,
the mass ratio of the aminosiloxane to the graphene oxide is (10-50): (0.5-5).
5. The graphene oxide-silicone-melamine hybrid according to claim 1, wherein the preparation method of the hydroxyl-modified melamine is as follows: mixing melamine and formaldehyde, regulating the pH value to 8-9, and reacting at 60-90 ℃ for 0.5-2h to obtain the hydroxyl modified melamine.
6. The graphene oxide-silicone-melamine hybrid according to claim 1 or 2, wherein the preparation method of the modified graphene oxide is as follows: adding ethanol solvent into graphene oxide, performing ultrasonic dispersion for 0.5-1h at 30-50 ℃, then dropwise adding aminosilicone, and performing stirring reflux reaction for 3-5h at 60-100 ℃ to obtain the modified graphene oxide.
7. A method of preparing a graphene oxide-silicone-melamine hybrid according to any one of claims 1-6, comprising the steps of:
and uniformly mixing hydroxyl modified melamine, a silicon-containing compound and modified graphene oxide, adding a catalyst, and performing hydrolytic condensation reaction at 30-60 ℃ for 3-8 hours to obtain the graphene oxide-organic silicon-melamine hybrid.
8. A flame retardant epoxy resin composite material, characterized in that it is prepared from the graphene oxide-silicone-melamine hybrid, epoxy resin, curing agent and curing catalyst according to any one of claims 1 to 6.
9. The flame retardant epoxy resin composite of claim 8, wherein the mass ratio of epoxy resin to graphene oxide-silicone-melamine hybrid is (90-110): (5-30), preferably 100: (5-30), more preferably 100: (10-25); and/or the number of the groups of groups,
the curing agent contains hydroxyl bonds or nitrogen hydrogen bonds, and the equivalent ratio of the hydroxyl bonds or the nitrogen hydrogen bonds of the curing agent to the epoxy groups of the epoxy resin is 1: (0.8-1.2); and/or the number of the groups of groups,
the curing agent is selected from one or more than two of phenolic resin, bisphenol A phenolic resin or 4,4' -diaminodiphenyl methane.
10. A method of preparing the flame retardant epoxy resin composite of claim 8 or 9, comprising the steps of:
adding graphene oxide-organic silicon-melamine hybrid into epoxy resin, stirring uniformly at room temperature, adding a curing agent and a curing catalyst, curing for 0.5-1.5h at 140-160 ℃, and then curing for 3-5h at 190-210 ℃ to obtain the flame-retardant epoxy resin composite material.
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