CN115010993A - Preparation method and application of graphene oxide hybrid flame retardant - Google Patents
Preparation method and application of graphene oxide hybrid flame retardant Download PDFInfo
- Publication number
- CN115010993A CN115010993A CN202210833229.8A CN202210833229A CN115010993A CN 115010993 A CN115010993 A CN 115010993A CN 202210833229 A CN202210833229 A CN 202210833229A CN 115010993 A CN115010993 A CN 115010993A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- graphene oxide
- preparation
- epoxy resin
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- 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 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims description 53
- 229920000647 polyepoxide Polymers 0.000 claims description 53
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000002131 composite material Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005303 weighing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910014299 N-Si Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
A preparation method of a graphene oxide hybrid flame retardant comprises the following steps: s1, preparing graphene oxide; s2, preparing an oligomer; and S3, putting the graphene oxide and the oligomer into an ethanol solution, carrying out surface grafting reaction at 50-80 ℃, standing for 3-6 h after the reaction is finished, carrying out reduced pressure suction filtration, washing with deionized water, and drying to obtain the flame retardant. According to the flame retardant disclosed by the invention, graphene powder is good in dispersibility, low in stacking degree and not easy to agglomerate through solvent heat treatment, oxygen-containing groups on the surface of the graphene powder are enhanced, and a nano hybrid structure is formed by further performing surface modification on the graphene oxide and the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, so that the flame retardant performance of the flame retardant is improved.
Description
Technical Field
The invention particularly relates to a preparation method and application of a graphene oxide hybrid flame retardant.
Background
The epoxy resin has good mechanical property, good heat resistance, high bonding strength, excellent insulating property and the like, and has good molding processability, strong component designability and low curing shrinkage rate, so the epoxy resin is widely applied to the fields of coatings, adhesives, casting materials, mold pressing materials, composite materials and the like. Moreover, many applications of epoxy resins are accompanied by heat exchange and temperature rise, and with the increasing requirements on the performance of epoxy resins and the increasing awareness of safety and environmental protection, the potential fire hazard of epoxy resin related products is attracting more and more attention. The epoxy resin mainly contains elements such as carbon, hydrogen and oxygen, belongs to an intrinsically flammable material, and can generate a large amount of dense smoke, toxic gas and molten droplets in the combustion process. Therefore, improving the flame retardant performance of epoxy resins is a key issue to be solved in epoxy resin applications.
In the research of flame retardant modification of epoxy resin, the flame retardant property of the epoxy resin is modified by adding special inorganic materials (phyllosilicate, graphene, metal oxide and the like) or organic compounds (elements containing phosphorus, nitrogen and the like) and the like, wherein the inorganic materials have good heat resistance and better heat insulation property and physical carbonization effect, and the organic compounds containing the elements containing phosphorus, nitrogen, silicon, boron and the like are substances with the most efficient flame retardant property after halogen flame retardants, so that the organic compounds are widely applied to flame retardant modification of polymers, and the flame retardant property of the epoxy resin is obviously improved after the organic compounds are added.
The organic type flame retardant or the inorganic type flame retardant after single modification may cause a significant decrease in mechanical or thermal properties of the epoxy resin. In recent years, organic-inorganic composite flame retardants are widely used in flame retardant polymer research, and particularly, inorganic nano materials are used as frameworks, such as carbon nanotubes, layered silicate, graphene, POSS, MOF and the like, and are functionally modified by organic compounds containing phosphorus, nitrogen, silicon and the like to prepare novel nano composite flame retardants. However, the preparation process of the novel flame retardant is complicated, and the compatibility of organic and inorganic interfaces needs to be improved, so that the mechanical property and the thermal property of the epoxy resin are influenced, and the wide application of the novel flame retardant is limited.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method and application of a graphene oxide hybrid flame retardant.
The technical scheme adopted by the embodiment of the invention for solving the technical problem is as follows:
a preparation method of a graphene oxide hybrid flame retardant comprises the following steps:
s1, adding oxalic acid and graphene powder into a mixed solution with the mass ratio of water to an alcohol solvent being 1:1 to prepare a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and reacting at 120-180 ℃ for 12-48 hours to prepare graphene oxide;
s2, adding an amino-containing silane coupling agent and paraformaldehyde into an organic solvent, uniformly dispersing, and carrying out condensation reflux reaction at the temperature of 40-60 ℃ for 6-12 h to obtain a pretreated substance; dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, dropwise adding the solution into a pretreated substance, raising the temperature to 60-90 ℃, and reacting for 6-12 hours to obtain an oligomer;
and S3, putting the graphene oxide and the oligomer into an ethanol solution, carrying out surface grafting reaction at 50-80 ℃, standing for 3-6 h after the reaction is finished, carrying out reduced pressure suction filtration, washing with deionized water, and drying to obtain the flame retardant.
Preferably, the alcoholic solvent includes one or more of methanol, ethanol, glycerol and ethylene glycol.
Preferably, the mass ratio of the oxalic acid to the graphene to the mixed solution is 0.01-0.05: 1: 50-100.
Preferably, the aminosilane-containing coupling agent comprises one of KH550, KH602, KH792 and KH 912.
Preferably, the organic solvent includes one of ethanol, dimethylformamide and dimethylsulfoxide.
Preferably, the molar ratio of the amino-containing silane coupling agent to the paraformaldehyde to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1-5: 1: 0.5-3.
Preferably, the mass ratio of the graphene oxide to the oligomer added in the third step is 1: 0.05-0.15.
A flame retardant is prepared by the preparation method.
Preferably, the application of the flame retardant comprises the following steps:
s1, mechanically stirring epoxy resin and the flame retardant at 40-60 ℃, adding a curing agent, and mechanically stirring under a vacuum condition to obtain an epoxy resin pre-cured product;
s2, pouring the epoxy resin pre-cured product into a mold, heating to perform a curing reaction, and cooling to room temperature after the reaction is finished to obtain the flame-retardant epoxy resin composite material.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation process of the flame retardant is simple, the process conditions are easy to control, the flame retardant with the dosage as low as 1-3% can play an excellent flame retardant effect, and the flame retardant is applied to the novel epoxy resin composite material due to small addition amount of the flame retardant, so that the operation procedures can be simplified, and the influence on the curing process can be reduced.
2. According to the invention, the graphene powder has good dispersibility and low stacking degree through solvent heat treatment, is not easy to agglomerate, the number of oxygen-containing groups on the surface of the graphene powder is increased, and the graphene powder and the oligomer are subjected to surface modification to form a nano hybrid structure, so that the comprehensive performance of the composite material is improved.
3. The flame retardant prepared by the invention has physical shielding effect, high char yield, high-efficiency flame retardance and high reactivity, and can be uniformly dispersed in epoxy resin and react when being combined with curing systems such as epoxy resin and the like, so that the interface compatibility is improved, the flame retardance, the mechanical property and the thermal property of the flame-retardant epoxy resin composite material are improved, the flame-retardant epoxy resin composite material reaches V-0 or V-1 grade in a vertical combustion test, and the LOI reaches about 30 percent.
Detailed Description
The scheme of the application is further described below with reference to specific examples:
example 1
S1, mixing water and an ethanol solvent in a mass ratio of 1:1 to form 100mL of mixed solution, dropwise adding 0.01g of oxalic acid and 1g of graphene powder into the mixed solution to prepare mixed solution, stirring uniformly, transferring the mixed solution into a high-pressure reaction kettle, and reacting at the temperature of 150 ℃ for 24 hours to obtain graphene oxide;
s2, adding 41.2g of amino-containing silane coupling agent KH602 and 6.0g of paraformaldehyde (the molar ratio is 1:1) into 200mL of ethanol, uniformly dispersing, and carrying out condensation reflux reaction at the temperature of 50 ℃ for 6 hours to obtain a pretreated substance; dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, dropwise adding the solution into a pretreated substance, heating the solution to 70 ℃, and reacting for 6 hours to obtain an oligomer;
s3, putting 2.0g of graphene oxide and 0.1g of oligomer prepared in the mass ratio of 1:0.05 into 100ml of ethanol solution for surface grafting reaction, reacting at 60 ℃ for 6h, standing for 3h after the reaction is finished, performing vacuum filtration, washing with deionized water for multiple times, and putting into a vacuum oven for drying to obtain the flame retardant.
Example 2
A preparation method of a graphene oxide hybridized epoxy resin flame retardant comprises the following steps:
s1, mixing water and an ethanol solvent in a mass ratio of 1:1 to form 100mL of mixed solution, dropwise adding 0.01g of oxalic acid and 1g of graphene powder into the mixed solution to prepare mixed solution, stirring uniformly, transferring the mixed solution into a high-pressure reaction kettle, and reacting at the temperature of 180 ℃ for 24 hours to obtain graphene oxide;
s2, adding 41.2g of amino-containing silane coupling agent KH602 and 6.0g of paraformaldehyde into 200mL of ethanol, uniformly dispersing, and carrying out condensation reflux reaction at the temperature of 60 ℃ for 6 hours to obtain a pretreated substance; dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, dropwise adding the solution into a pretreated substance, heating the solution to 80 ℃, and reacting for 6 hours to obtain an oligomer;
s3, putting the prepared graphene oxide and the prepared low polymer into an ethanol solution according to the mass ratio of 1:0.05 for surface grafting reaction, reacting for 6 hours at 80 ℃, standing for 3 hours after the reaction is finished, washing with deionized water for multiple times after reduced pressure suction filtration, and putting into a vacuum oven for drying to obtain the flame retardant.
Example 3
A preparation method of a graphene oxide hybridized epoxy resin flame retardant comprises the following steps:
s1, mixing water and an ethanol solvent in a mass ratio of 1:1 to form 150mL of mixed solution, dropwise adding 0.03g of oxalic acid and 2g of graphene powder into the mixed solution to prepare mixed solution, stirring uniformly, transferring the mixed solution into a high-pressure reaction kettle, and reacting at the temperature of 150 ℃ for 24 hours to obtain graphene oxide;
s2, adding 41.2g of amino-containing silane coupling agent KH602 and 6.0g of paraformaldehyde into 200mL of ethanol, uniformly dispersing, and carrying out condensation reflux reaction at the temperature of 60 ℃ for 6 hours to obtain a pretreated substance; dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, dropwise adding the solution into a pretreated substance, heating the solution to 70 ℃, and reacting for 6 hours to obtain an oligomer;
s3, putting the prepared graphene oxide and the oligomer into an ethanol solution according to the mass ratio of 1:0.1 for surface grafting reaction, reacting at 80 ℃ for 10 hours, standing for 5 hours after the reaction is finished, washing with deionized water for multiple times after pressure reduction and suction filtration, and putting into a vacuum oven for drying to obtain the graphene oxide hybrid flame retardant.
The molecular structural formula of the oligomer obtained by reacting the KH602 amino-containing coupling agent with paraformaldehyde in an ethanol solution is as follows:
application example 1
Weighing 80 parts by mass of epoxy resin CYD-128, 20 parts by mass of DDM curing agent and 1 part by mass of graphene oxide hybrid flame retardant prepared in example 1, mechanically stirring at 70 ℃ in vacuum for 30min, then pouring the mixture into a mold, and curing through a programmed temperature rise process of 100 ℃/2h +130 ℃/2h to obtain the flame-retardant modified epoxy resin composite material.
Application example 2
Weighing 80 parts by mass of epoxy resin CYD-128, 20 parts by mass of DDM curing agent and 2 parts by mass of graphene oxide hybrid flame retardant prepared in the embodiment 2, mechanically stirring for 30min at 70 ℃, then pouring the mixture into a mold, and curing through a programmed heating process of 100 ℃/2h +130 ℃/2h to obtain the flame-retardant modified epoxy resin composite material.
Application example 3
Weighing 80 parts by mass of epoxy resin CYD-128, 20 parts by mass of DDM curing agent and 5 parts by mass of graphene oxide hybrid flame retardant prepared in the embodiment 3, mechanically stirring at 70 ℃ in vacuum for 30min, then pouring the mixture into a mold, and curing through a programmed heating process of 100 ℃/2h +130 ℃/2h to obtain the flame-retardant modified epoxy resin composite material.
Application example 4
Weighing 80 parts by mass of epoxy resin CYD-128, 20 parts by mass of DDS curing agent and 2 parts by mass of graphene oxide hybrid flame retardant prepared in example 2, mechanically stirring at 70 ℃ in vacuum for 30min, then pouring the mixture into a mold, and curing by a programmed heating process of 100 ℃/2h +130 ℃/2h to obtain the flame-retardant modified epoxy resin composite material.
Comparative example 1 (No flame retardant added, curing agent DDM)
Weighing 80 parts by mass of epoxy resin CYD-128 and 20 parts by mass of DDM curing agent, mechanically stirring for 30min at 70 ℃, then pouring the epoxy resin CYD-128 and DDM curing agent into a mold, and curing by a programmed heating process of 100 ℃/2h +130 ℃/2h to obtain an epoxy resin cured product.
Comparative example 2 (No flame retardant added, curing agent DDS)
Weighing 80 parts by mass of epoxy resin CYD-128 and 20 parts by mass of DDS curing agent, mechanically stirring for 30min at 70 ℃, then pouring the mixture into a mold, and curing by a programmed heating process of 100 ℃/2h +150 ℃/2h +180 ℃/3h to obtain an epoxy resin cured product.
Comparative example 3 (graphene oxide as modifier and curing agent DDM)
Weighing 80 parts by mass of epoxy resin CYD-128, 20 parts by mass of DDM curing agent and 2 parts by mass of graphene oxide, mechanically stirring for 30min at 70 ℃, then pouring the mixture into a mold, and curing through a programmed heating process of 100 ℃/2h +130 ℃/2h to obtain the flame-retardant modified epoxy resin composite material.
Comparative example 4 (oligomer as modifier and curing agent DDM)
Weighing 80 parts by mass of epoxy resin CYD-128, 20 parts by mass of DDM curing agent and 2 parts by mass of oligomer, mechanically stirring for 30min at 70 ℃, then pouring the mixture into a mold, and curing through a programmed heating process of 100 ℃/2h +130 ℃/2h to obtain the flame-retardant modified epoxy resin composite material.
Test effects
In order to verify the flame retardant effect of the epoxy resin composite material prepared from the graphene oxide hybridized epoxy resin flame retardant, a comparative test was carried out. The comparative examples 1 to 4 and application examples 1 to 4 were tested for LOI, UL-94, impact strength and heat distortion temperature. The results are shown in the following table:
| application example | Curing agent | LOI％ | UL-94 | Impact strength kJ/m 2 | Heat distortion temperature DEG C |
| Comparative example 1 | DDM | 22 | NR | 25.9±2.1 | 150 |
| Comparative example 2 | DDS | 23 | NR | 26.6±2.7 | 156 |
| Comparative example 3 | DDM | 21 | NR | 29.1±3.3 | 154 |
| Comparative example 4 | DDM | 26 | V-2 | 28.3±3.1 | 153 |
| Application example 1 | DDM | 30.5 | V-1 | 30.2±2.9 | 154 |
| Application example 2 | DDM | 31.3 | V-0 | 31.5±3.4 | 157 |
| Application example 3 | DDM | 32.6 | V-0 | 33.6±3.8 | 155 |
| Application example 4 | DDS | 31.5 | V-0 | 31.9±2.7 | 159 |
Experimental results show that the LOI values of the flame-retardant modified epoxy resin composite materials of the application examples 1-4 are all higher than those of the comparative examples 1-4, and the higher the LOI value is, the better the flame retardant property is, and the flame retardant properties of the epoxy resin composite materials of the application examples 1-4 are all better than those of the epoxy resin composite materials of the comparative examples 1-4. The graphene oxide and the oligomer are respectively and independently added in the comparative example 3 and the comparative example 4 to prepare the flame-retardant modified epoxy resin composite material, and the graphene oxide and the oligomer are added in the application examples 1-4 to carry out surface grafting reaction to form a new flame retardant, and experimental results show that the graphene oxide and the P-N-Si organic compound form a better synergistic effect and have an interface effect with the epoxy resin, so that the comprehensive performance of the epoxy resin composite material is obviously improved.
The foregoing is only a preferred embodiment of the invention, it being understood that the invention is not limited to the forms herein described, nor is it to be construed as excluding other embodiments, and that it is intended to cover various other combinations and modifications, which are within the scope of the concept herein disclosed, and which are obvious to those skilled in the relevant art and many modifications. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a graphene oxide hybrid flame retardant is characterized by comprising the following steps:
s1, adding oxalic acid and graphene powder into a mixed solution with the mass ratio of water to an alcohol solvent being 1:1 to prepare a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and reacting at 120-180 ℃ for 12-48 hours to prepare graphene oxide;
s2, putting 41.2g of amino-containing silane coupling agent and 6.0g of paraformaldehyde into 200ml of organic solvent, uniformly dispersing, and carrying out condensation reflux reaction at the temperature of 40-60 ℃ for 6-12 h to obtain a pretreatment substance; dissolving 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in an organic solvent, dropwise adding the solution into a pretreated substance, raising the temperature to 60-90 ℃, and reacting for 6-12 hours to obtain an oligomer;
s3, putting the prepared graphene oxide and the prepared low polymer into 100ml of ethanol solution according to the mass ratio of 1:0.05, carrying out surface grafting reaction at 50-80 ℃, standing for 3-6 h after the reaction is finished, carrying out reduced pressure suction filtration, washing with deionized water, and drying to obtain the flame retardant.
2. The preparation method of the graphene oxide hybrid flame retardant according to claim 1, wherein the alcohol solvent comprises one or more of methanol, ethanol, glycerol and ethylene glycol.
3. The preparation method of the graphene oxide hybrid flame retardant according to claim 1, wherein the mass ratio of the oxalic acid to the graphene to the mixed solution is 0.01-0.05: 1: 50-100.
4. The preparation method of the graphene oxide hybrid flame retardant according to claim 1, wherein the amino silane-containing coupling agent comprises one of KH550, KH602, KH792 and KH 912.
5. The preparation method of the graphene oxide hybrid flame retardant according to claim 1, wherein the organic solvent comprises one of ethanol, dimethylformamide and dimethylsulfoxide.
6. The preparation method of the graphene oxide hybrid flame retardant according to claim 1, wherein the molar ratio of the amino-containing silane coupling agent to paraformaldehyde to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1-5: 1: 0.5-3.
7. The preparation method of the graphene oxide hybrid flame retardant according to claim 1, wherein the mass ratio of the graphene oxide to the oligomer added in the third step is 1: 0.05-0.15.
8. A flame retardant produced by the production method according to claim 1.
9. Use of a flame retardant according to claim 8, comprising the steps of:
s1, mechanically stirring epoxy resin and a flame retardant at 40-60 ℃, adding a curing agent, and mechanically stirring under a vacuum condition to obtain an epoxy resin pre-cured product;
s2, pouring the epoxy resin pre-cured product into a mold, heating to perform a curing reaction, and cooling to room temperature after the reaction is finished to obtain the flame-retardant epoxy resin composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210833229.8A CN115010993A (en) | 2022-07-14 | 2022-07-14 | Preparation method and application of graphene oxide hybrid flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210833229.8A CN115010993A (en) | 2022-07-14 | 2022-07-14 | Preparation method and application of graphene oxide hybrid flame retardant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115010993A true CN115010993A (en) | 2022-09-06 |
Family
ID=83081501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210833229.8A Pending CN115010993A (en) | 2022-07-14 | 2022-07-14 | Preparation method and application of graphene oxide hybrid flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115010993A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185706A (en) * | 2021-06-01 | 2021-07-30 | 韩光军 | Flame-retardant additive, flame-retardant ABS plastic containing additive and preparation method |
| CN115305619A (en) * | 2022-10-11 | 2022-11-08 | 江苏红金顶织造有限公司 | High-strength textile fabric with flame-retardant effect and preparation method thereof |
| CN116102820A (en) * | 2022-12-23 | 2023-05-12 | 理工清科(重庆)先进材料研究院有限公司 | Metal-MPOFs/polymer composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440788A (en) * | 2018-03-15 | 2018-08-24 | 厦门大学 | A kind of preparation method of containing phosphorus silicon functional graphene oxide |
| CN113004734A (en) * | 2021-03-02 | 2021-06-22 | 深圳市捷路安科技发展有限公司 | Functionalized graphene flame-retardant epoxy resin floor paint and preparation method thereof |
| US20210309831A1 (en) * | 2018-08-15 | 2021-10-07 | Chemische Fabrik Budenheim Kg | Polymer composition containing a phosphonate flame retardant |
| CN114426701A (en) * | 2022-01-11 | 2022-05-03 | 桂林理工大学 | Preparation of P-N compound and graphene oxide synergistic flame retardant and application of P-N compound and graphene oxide synergistic flame retardant in epoxy resin |
-
2022
- 2022-07-14 CN CN202210833229.8A patent/CN115010993A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440788A (en) * | 2018-03-15 | 2018-08-24 | 厦门大学 | A kind of preparation method of containing phosphorus silicon functional graphene oxide |
| US20210309831A1 (en) * | 2018-08-15 | 2021-10-07 | Chemische Fabrik Budenheim Kg | Polymer composition containing a phosphonate flame retardant |
| CN113004734A (en) * | 2021-03-02 | 2021-06-22 | 深圳市捷路安科技发展有限公司 | Functionalized graphene flame-retardant epoxy resin floor paint and preparation method thereof |
| CN114426701A (en) * | 2022-01-11 | 2022-05-03 | 桂林理工大学 | Preparation of P-N compound and graphene oxide synergistic flame retardant and application of P-N compound and graphene oxide synergistic flame retardant in epoxy resin |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185706A (en) * | 2021-06-01 | 2021-07-30 | 韩光军 | Flame-retardant additive, flame-retardant ABS plastic containing additive and preparation method |
| CN113185706B (en) * | 2021-06-01 | 2022-12-20 | 深圳市嘉凯勒实业有限公司 | Flame-retardant additive, flame-retardant ABS plastic containing additive and preparation method |
| CN115305619A (en) * | 2022-10-11 | 2022-11-08 | 江苏红金顶织造有限公司 | High-strength textile fabric with flame-retardant effect and preparation method thereof |
| CN116102820A (en) * | 2022-12-23 | 2023-05-12 | 理工清科(重庆)先进材料研究院有限公司 | Metal-MPOFs/polymer composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115010993A (en) | Preparation method and application of graphene oxide hybrid flame retardant | |
| CN110510605B (en) | Nitrogen-rich group functionalized graphene, and preparation method and application thereof | |
| CN109180952B (en) | Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof | |
| CN109467574B (en) | Reactive flame retardant based on vanillin as well as preparation and application thereof | |
| CN110256814B (en) | Preparation method of piperazine structure-containing DOPO derivative modified flame-retardant epoxy resin | |
| CN112300538B (en) | Preparation method of novel inorganic-organic hybrid flame-retardant epoxy resin material | |
| CN115505222B (en) | High-heat-conductivity halogen-free flame-retardant polystyrene composite material and preparation method thereof | |
| CN114231041A (en) | B1-grade flame-retardant ceramic low-smoke silicone rubber cable material and preparation method thereof | |
| CN111500234A (en) | Flame-retardant epoxy resin halogen-free potting material and preparation method thereof | |
| CN113881192A (en) | Low-smoke flame-retardant epoxy resin composite material and preparation method thereof | |
| CN111635618A (en) | Phosphazene-based organic metal complex flame-retardant epoxy resin and preparation method thereof | |
| CN110156958B (en) | Bio-based phosphaphenanthrene curing agent flame-retardant epoxy resin material and preparation method thereof | |
| CN103194063A (en) | Trapezoidal polysiloxane modified thermosetting resin and preparation method thereof | |
| CN113683638A (en) | Phosphorus-containing organic acid alkenyl amine salt and preparation method and application thereof | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN116656008A (en) | Preparation method, product and application of microcapsule type hollow mesoporous silica flame retardant | |
| CN116478065A (en) | Preparation of biomass epoxy resin with degradable and flame-retardant characteristics | |
| CN113292823B (en) | Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material | |
| CN109575076B (en) | Preparation of phosphorus-containing bismaleimide and application of phosphorus-containing bismaleimide in flame-retardant epoxy resin | |
| CN109553929B (en) | Nano flame-retardant epoxy resin composite material and preparation method thereof | |
| CN113462154A (en) | High-heat-resistance cyanate resin and preparation method thereof | |
| KR20220088019A (en) | Thermosetting resin composition with high toughness and flame retardant | |
| CN112321800A (en) | Preparation method of flame-retardant epoxy resin | |
| CN115850708B (en) | Preparation method and application of N-P-Si-containing caged polysilsesquioxane flame retardant | |
| CN114106527B (en) | Anti-dripping halogen-free flame-retardant PBT-based composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220906 |