CN107815116B - Graphene hybrid particle flame retardant and preparation method and application thereof - Google Patents
Graphene hybrid particle flame retardant and preparation method and application thereof Download PDFInfo
- Publication number
- CN107815116B CN107815116B CN201711072812.7A CN201711072812A CN107815116B CN 107815116 B CN107815116 B CN 107815116B CN 201711072812 A CN201711072812 A CN 201711072812A CN 107815116 B CN107815116 B CN 107815116B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- poss
- graphene
- hybrid particle
- graphene hybrid
- 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.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 95
- 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 91
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- 239000002245 particle Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- -1 POSS Substances 0.000 claims abstract description 28
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000003993 interaction Effects 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 229920000098 polyolefin Polymers 0.000 claims abstract description 4
- 238000005342 ion exchange Methods 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 11
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical group FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910020808 NaBF Inorganic materials 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011852 carbon nanoparticle Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- 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
The invention discloses a graphene hybrid particle flame retardant and a preparation method and application thereof. The method is characterized in that active POSS reacts with N-alkylamine to realize ionization, and POSS-based quaternary ammonium salt ionic liquid is prepared through ion exchange reaction; and (3) constructing the graphene hybrid particle flame retardant by the interaction of the POSS-based quaternary ammonium salt ionic liquid and pi-pi and pi-cation of graphene. The prepared graphene hybrid particle flame retardant is a halogen-free environment-friendly flame retardant, POSS, ionic liquid and graphene have different flame retardant elements and mechanisms, and can generate a synergistic effect, the limit oxygen index of PS can be improved to 26.5% by adding 5% of the flame retardant synthesized by the invention, the limit oxygen index of PP can be improved to 25.9% by adding 5% of the flame retardant synthesized by the invention, the flame retardant is obviously better than a commercially available organic silicon flame retardant, and the graphene hybrid particle flame retardant can be used as an additive for a polyolefin polymer flame retardant, is simple and convenient to operate and is easy to control.
Description
Technical Field
The invention relates to a graphene hybrid particle flame retardant and a preparation method and application thereof.
Background
Graphene is a two-dimensional carbon nanoparticle, has a unique structure and good heat conduction and flame retardant properties, and in recent years, graphene is gradually developed into a novel flame retardant system, so that revolutionary influence is brought to the development of flame retardants. Compared with the traditional flame retardant material, a small amount of graphene can obviously reduce the maximum decomposition rate of the high polymer material, delay the combustion process and reduce the smoke generation rate, thereby improving the flame retardant property of the material. However, when graphene is used as a single flame retardant system, the flame retardant efficiency is not high, and therefore, in order to improve the flame retardant efficiency of graphene, graphene and other flame retardants need to be compounded to realize synergistic flame retardant. At present, researchers compound graphene with a plurality of flame retardant materials, such as nanoclay, magnesium hydroxide, hydrotalcite, ammonium polyphosphate, transition metal oxide, an intumescent flame retardant system and the like, to prepare a hybrid flame retardant system, and researches show that most hybrid flame retardant systems show a synergistic effect and have high-efficiency flame retardant performance. The method for compounding the graphene and other flame retardants mainly comprises two methods of chemical bond grafting and physical blending, wherein the chemical bond grafting can realize molecular-level compounding and has high stability, but the process is complex, oxygen-containing groups must be introduced to destroy the integrity of carbon nanoparticles, and the physical blending method is simple to operate, but effective compounding is difficult to realize and the structure is not adjustable. Therefore, it is important to select a flame-retardant system having a synergistic effect with graphene and realize effective compounding of the flame-retardant system.
Recently, application research of polyhedral oligomeric silsesquioxane (POSS) and ionic liquid in composite materials is carried out, and the ionic liquid with a regular structure can be prepared by utilizing the POSS structure, has better thermal stability and flame retardance, can reduce heat release during polymer combustion and promote generation of a high-oxidation-resistance cracking carbon layer. In order to further exert the flame retardant effect of POSS, ionic liquid and graphene, a novel hybrid graphene flame retardant is prepared by utilizing pi-pi and pi-cation interaction between POSS-based ionic liquid and graphene, the flame retardant has high stability and structural controllability, and can realize efficient flame retardance of a system, and the flame retardant is not reported at home and abroad.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a graphene hybrid particle flame retardant, and a preparation method and application thereof. According to the invention, POSS is taken as a nucleus to synthesize quaternary ammonium salt ionic liquid, and pi-pi and pi-cation interaction between the ionic liquid and graphene is utilized to construct hybrid particles, so that synergistic flame retardance of POSS, the ionic liquid and graphene is realized.
The graphene hybrid particle flame retardant is characterized in that the structure is shown as the formula (III):
wherein R is methyl, ethyl, propyl or butyl.
The preparation method of the graphene hybrid particle flame retardant is characterized in that active POSS shown as a formula (I) is reacted with N-alkylamine to realize ionization, and POSS-based quaternary ammonium salt ionic liquid shown as a formula (II) is prepared through ion exchange reaction; the interaction of POSS-based quaternary ammonium salt ionic liquid and pi-pi and pi-cation of graphene constructs the graphene hybrid particle flame retardant shown in the formula (III),
the active POSS is single-arm chlorobenzyl ethyl isobutyl polyhedral oligomeric silsesquioxane (POSS), and the structure of the POSS is shown as the formula (I):
the POSS-based quaternary ammonium salt ionic liquid has a structure shown in a formula (II):
in the formula (II), X－Is tetrafluoroborate (BF)4 －) Hexafluorophosphate radical (PF)6 －) Or bis (trifluoromethanesulfonyl) imide group ((F)3SO2)2N－Abbreviated TF2N－). R is methyl (-CH)3) Ethyl (-C)2H5) Propyl (-C)3H7) And butyl (-C)4H9）。
The preparation method of the graphene hybrid particle flame retardant is characterized by comprising the following specific steps:
dissolving active POSS in a solvent I, adding N-alkylamine and a catalyst, stirring and reacting at 80-82 ℃ for 16-24 hours, adding an anion salt into a reaction solution after the reaction is finished, stirring and reacting at 20-30 ℃ for 16-24 hours, obtaining a reaction solution a after the reaction is finished, pouring the reaction solution a into a solvent II to obtain a mixed solution, separating out a solid product from the mixed solution, and performing suction filtration, washing and vacuum drying on a filter cake of the obtained mixed solution to obtain the POSS-based quaternary ammonium salt ionic liquid shown in the formula II; and (3) dissolving the POSS-based quaternary ammonium salt ionic liquid and graphene in a solvent III, stirring and reacting for 6-12 hours at 150 ℃ to obtain a reaction liquid b, and decompressing, distilling and vacuum-drying a filter cake to obtain the graphene hybrid particle flame retardant shown in the formula (III).
The preparation method of the graphene hybrid particle flame retardant is characterized in that N-alkylamine is one of trimethylamine, triethylamine or tripropylamine, and the mass ratio of the active POSS to the N-alkylamine is 1:1-3, preferably 1: 2.
The preparation method of the graphene hybrid particle flame retardant is characterized in that the catalyst is sodium iodide or potassium iodide, and the mass ratio of the active POSS to the catalyst is 1:0.2-1, preferably 1: 0.5.
The preparation method of the graphene hybrid particle flame retardant is characterized in that the anion salt is sodium tetrafluoroborate (NaBF)4) Potassium hexafluorophosphate (KPF)6) Lithium bis (trifluoromethanesulfonyl) imide (LiNTF)2) One of (1); the ratio of the quantity of the active POSS to the quantity of the anionic salt is 1:1-3, and the preferred quantity is 1: 2.
The preparation method of the graphene hybrid particle flame retardant is characterized in that a solvent I is one of Acetonitrile (ACN), isopropanol and N, N-Dimethylformamide (DMF), preferably acetonitrile, and the volume consumption of the solvent I is 20-50mL/mmol based on the amount of the active POSS substance.
The preparation method of the graphene hybrid particle flame retardant is characterized in that the solvent II is one of water, ethanol and methanol, and preferably water; the volume of the solvent II is 30-50mL/mmol based on the amount of the active POSS material.
The preparation method of the graphene hybrid particle flame retardant is characterized in that a solvent III is propylene carbonate, and the volume consumption of the solvent III is 50-100mL/g based on the mass of graphene.
The preparation method of the graphene hybrid particle flame retardant is characterized in that the mass ratio of the POSS-based quaternary ammonium salt ionic liquid to the graphene is 3-1:1, preferably 2: 1.
The graphene hybrid particle flame retardant is applied to preparation of a polyolefin polymer flame retardant as an additive.
By adopting the technology, compared with the prior art, the invention has the beneficial effects that:
1) the prepared graphene hybrid particle flame retardant is a halogen-free environment-friendly flame retardant, POSS, ionic liquid and graphene have different flame retardant elements and mechanisms, and can generate a synergistic effect, the Limit Oxygen Index (LOI) of PS can be improved to 26.5% by adding 5% of the flame retardant synthesized by the invention, and the Limit Oxygen Index (LOI) of PP can be improved to 25.9% by adding 5% of the flame retardant synthesized by the invention, which is obviously better than that of a commercially available organic silicon flame retardant;
2) the graphene hybrid particle flame retardant prepared by the invention can be used as an additive for a polyolefin polymer flame retardant, and is simple and convenient to operate and easy to control.
Drawings
FIG. 1 POSS- [ TEA ] in example 1][PF6]Is/are as follows1H NMR spectrum;
FIG. 2 POSS- [ TEA ] in example 1][PF6]Infrared spectrum of (1).
Detailed Description
The technical solution of the present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto.
Comparative example 1:
specimens were prepared from 2.5 g of the silicone flame retardant SFR-100 (commercially available) and 47.5 g of GPPS at 200 ℃ by means of a microinjector and tested for a limiting oxygen index of 23.2%.
Comparative example 2:
specimens were prepared from 2.5 g of the silicone flame retardant SFR-100 (commercially available) and 47.5 g of PP at 200 ℃ using a mini-injector and tested for a limiting oxygen index of 23.1%.
Example 1:
9.70 g (0.01 mol) of one-armed chlorobenzylethyl isobutyl polyhedral oligomeric silsesquioxane (POSS) is dissolved in 300ml of acetonitrile, 2.02 g (0.02 mol) of triethylamine and 0.75 g (0.005 mol) of sodium iodide (NaI) are added, the mixture is stirred and reacted at 80 ℃ for 24 hours, and 3.68 g (0.02 mol) of potassium hexafluorophosphate (KPF) is added into the reaction solution after the reaction is finished6) Stirring at 20-30 deg.CStirring and reacting for 16 hours, pouring the obtained reaction liquid into 300ml of water after the reaction is finished to separate out a solid product, carrying out suction filtration, washing and vacuum drying on the obtained mixed liquid to obtain 9.34 g of POSS amine salt ionic liquid, which is abbreviated as POSS- [ TEA [ ]][PF6]The yield was 79.1%, the structure of the product prepared was confirmed,1the H NMR spectrum is shown in figure 1, and the prepared product FIIR R spectrum is shown in figure 2. 4 g of POSS- [ TEA ] were taken][PF6]Dissolving Graphene Oxide (GO) 2 g in Propylene Carbonate (PC) 300ml, stirring and reacting at 150 ℃ for 12 hours, decompressing and distilling the obtained reaction liquid after the reaction is finished, and drying a filter cake in vacuum to obtain a product 5.67 g of graphene hybrid particle flame retardant, namely RGO/POSS- [ TEA ]][PF6]The yield was 94.5%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of GPPS at 200 ℃ using a micro extruder and a micro injector, and the limiting oxygen index was measured to be 26.5%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of PP at 200 ℃ using a micro-extruder and a micro-injector, and the limiting oxygen index was tested to be 25.9%.
Example 2:
9.70 g (0.01 mol) of one-armed chlorobenzylethyl isobutyl polyhedral oligomeric silsesquioxane (POSS) is dissolved in 200ml of acetonitrile, 1.18 g (0.02 mol) of trimethylamine and 0.75 g (0.005 mol) of sodium iodide (NaI) are added, the mixture is stirred and reacted for 16 hours at 82 ℃, and 2.20 g (0.02 mol) of sodium tetrafluoroborate (NaBF) is added into the reaction solution after the reaction is finished4) Stirring and reacting for 24 hours at the temperature of 20-30 ℃, pouring the obtained reaction liquid into 500ml of water after the reaction is finished to separate out a solid product, carrying out suction filtration and washing on the obtained mixed liquid, and carrying out vacuum drying on a filter cake to obtain 7.80 g of POSS amine salt ionic liquid, which is abbreviated as POSS- [ TMA [ ] -][BF4]Yield 72.2%. Taking 4 g POSS- [ TMA [ ]][BF4]Dissolving Graphene Oxide (GO) 2 g in Propylene Carbonate (PC) 150ml, stirring and reacting for 6 hours at 150 ℃, decompressing and distilling the obtained reaction liquid after the reaction is finished, and drying a filter cake in vacuum to obtain a product 5.82 g of graphene hybrid particle flame retardant, which is abbreviated as RGO/POSS- [ TMA][BF4]The yield was 97%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of GPPS at 200 ℃ using a micro extruder and a micro injector, and the limiting oxygen index was measured to be 26.1%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of PP at 200 ℃ using a micro-extruder and a micro-injector, and the limiting oxygen index was tested to be 25.5%.
Example 3:
9.70 g (0.01 mol) of single-arm chlorobenzyl ethyl isobutyl polyhedral oligomeric silsesquioxane (POSS) is dissolved in 500ml of acetonitrile, 2.87 g (0.02 mol) of triethylamine and 0.83 g (0.005 mol) of potassium iodide (KI) are added, the mixture is stirred and reacted for 20 hours at 82 ℃, and 5.74 g (0.02 mol) of lithium bis (trifluoromethanesulfonyl) imide (LiNTF) is added into the reaction solution after the reaction is finished2) Stirring and reacting for 20 hours at 20-30 ℃, pouring the obtained reaction liquid into 400ml of water after the reaction is finished to separate out a solid product, performing suction filtration and washing on the obtained mixed liquid, and performing vacuum drying on a filter cake to obtain 7.89 g of POSS (polyhedral oligomeric silsesquioxane) amine salt ionic liquid, which is abbreviated as POSS- [ TEA (ethylene-based polyethylene terephthalate) ]][NTF2]The yield was 60.2%. 3 g of POSS- [ TEA ] were taken][NTF2]Dissolving 3 g of Graphene Oxide (GO) in 200ml of Propylene Carbonate (PC), stirring and reacting for 9 hours at 150 ℃, decompressing and distilling the obtained reaction liquid after the reaction is finished, and drying a filter cake in vacuum to obtain a product 5.71 g of graphene hybrid particle flame retardant, namely RGO/POSS- [ TEA ]][NTF2]The yield was 95.2%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of GPPS at 200 ℃ using a micro extruder and a micro injector, and the limiting oxygen index was measured to be 26.0%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of PP at 200 ℃ using a micro-extruder and a micro-injector, and the limiting oxygen index was tested to be 25.7%.
Example 4:
9.67 g (0.01 mol) of one-armed chlorobenzylethyl isobutyl polyhedral oligomeric silsesquioxane (POSS) was dissolved in 300ml of acetonitrile, 2.87 g (0.02 mol) of tripropylamine and 0.83 g (0.005 mol) of potassium iodide (KI) were added, and the reaction was stirred at 82 ℃ to reactAfter the reaction was completed for 24 hours, 3.68 g (0.02 mol) of potassium hexafluorophosphate (KPF) was further added to the reaction mixture6) Stirring and reacting for 24 hours at 20-30 ℃, pouring the obtained reaction liquid into 500ml of water after the reaction is finished to separate out a solid product, carrying out suction filtration and washing on the obtained mixed liquid, and carrying out vacuum drying on a filter cake to obtain 10.04 g of POSS (polyhedral oligomeric silsesquioxane) amine salt ionic liquid, which is abbreviated as POSS- [ TPA (terephthalic acid)][PF6]Yield 82.1%. Taking 3 g of POSS- [ TPA][PF6]Dissolving 3 g of Graphene Oxide (GO) in 300ml of Propylene Carbonate (PC), stirring and reacting for 12 hours at 150 ℃, decompressing and distilling the obtained reaction liquid after the reaction is finished, and drying a filter cake in vacuum to obtain a product 5.55 g of graphene hybrid particle flame retardant, which is abbreviated as RGO/POSS- [ TPA][PF6]The yield was 92.5%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of GPPS at 200 ℃ using a micro extruder and a micro injector, and the limiting oxygen index was tested to be 25.8%.
Sample bars were prepared from 2.5 g of graphene hybrid particle flame retardant and 47.5 g of PP at 200 ℃ using a micro extruder and a micro injector, and the limiting oxygen index was tested to be 25.3%.
The influence of the graphene hybrid particle flame retardant prepared by the invention and a commercially available silane flame retardant SFR-100 on the limiting oxygen index of GPPS and PP is shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the graphene hybrid particle flame retardant prepared by the invention has an obvious flame retardant effect on GPPS and PP, and the effect of the graphene hybrid particle flame retardant is superior to that of SFR-100.
Claims (16)
1. A graphene hybrid particle flame retardant is characterized in that the structure is shown as formula (III):
the POSS-based quaternary ammonium salt ionic liquid is constructed by the interaction of the POSS-based quaternary ammonium salt ionic liquid shown in the formula (II) and pi-pi and pi-cation of graphene, and the structure of the POSS-based quaternary ammonium salt ionic liquid is shown in the formula (II):
in the formulae (II) and (III),
is tetrafluoroborate (BF)4 －) Hexafluorophosphate radical (PF)6 －) Or bis (trifluoromethanesulfonyl) imide group ((F)3SO2)2N－Abbreviated TF2N－) (ii) a R is methyl (-CH)3) Ethyl (-C)2H5) Propyl (-C)3H7) Or butyl (-C)4H9）。
2. The preparation method of the graphene hybrid particle flame retardant according to claim 1 is characterized in that active POSS shown as a formula (I) is reacted with N-alkylamine to realize ionization, and POSS-based quaternary ammonium salt ionic liquid shown as a formula (II) is prepared through ion exchange reaction; the interaction of POSS-based quaternary ammonium salt ionic liquid and pi-pi and pi-cation of graphene constructs the graphene hybrid particle flame retardant shown in the formula (III),
the active POSS is single-arm chlorobenzyl ethyl isobutyl polyhedral oligomeric silsesquioxane (POSS), and the structure of the POSS is shown as the formula (I):
the POSS-based quaternary ammonium salt ionic liquid has a structure shown in a formula (II):
in the formula (II), the compound is shown in the specification,
is tetrafluoroborate (BF)4 －) Hexafluorophosphate radical (PF)6 －) Or bis (trifluoromethanesulfonyl) imide group ((F)3SO2)2N－Abbreviated TF2N－) (ii) a R is methyl (-CH)3) Ethyl (-C)2H5) Propyl (-C)3H7) Or butyl (-C)4H9）。
3. The preparation method of the graphene hybrid particle flame retardant according to claim 2, which is characterized by comprising the following steps:
dissolving active POSS in a solvent I, adding N-alkylamine and a catalyst, stirring and reacting at 80-82 ℃ for 16-24 hours, adding an anion salt into a reaction solution after the reaction is finished, stirring and reacting at 20-30 ℃ for 16-24 hours, obtaining a reaction solution a after the reaction is finished, pouring the reaction solution a into a solvent II to obtain a mixed solution, separating out a solid product from the mixed solution, and performing suction filtration, washing and vacuum drying on a filter cake of the obtained mixed solution to obtain the POSS-based quaternary ammonium salt ionic liquid shown in the formula II; and (3) dissolving the POSS-based quaternary ammonium salt ionic liquid and graphene in a solvent III, stirring and reacting for 6-12 hours at 150 ℃ to obtain a reaction liquid b, and decompressing, distilling and vacuum-drying a filter cake to obtain the graphene hybrid particle flame retardant shown in the formula (III).
4. The preparation method of the graphene hybrid particle flame retardant according to claim 3, wherein the N-alkylamine is one of trimethylamine, triethylamine or tripropylamine, and the mass ratio of the active POSS to the N-alkylamine is 1: 1-3.
5. The preparation method of the graphene hybrid particle flame retardant of claim 3, wherein the catalyst is sodium iodide or potassium iodide, and the ratio of the amount of the active POSS to the amount of the catalyst is 1: 0.2-1.
6. The method for preparing graphene hybrid particle flame retardant according to claim 3, wherein the anion salt is sodium tetrafluoroborate (NaBF)4) Potassium hexafluorophosphate (KPF)6) Lithium bis (trifluoromethanesulfonyl) imide (LiNTF)2) One of (1); the mass ratio of the active POSS to the anionic salt is 1: 1-3.
7. The preparation method of the graphene hybrid particle flame retardant according to claim 3, wherein the solvent I is one of Acetonitrile (ACN), isopropanol and N, N-Dimethylformamide (DMF), and the volume usage of the solvent I is 20-50mL/mmol based on the amount of the active POSS substance.
8. The preparation method of the graphene hybrid particle flame retardant according to claim 3, wherein the solvent II is one of water, ethanol and methanol; the volume of the solvent II is 30-50mL/mmol based on the amount of the active POSS material.
9. The preparation method of the graphene hybrid particle flame retardant according to claim 3, characterized in that the solvent III is propylene carbonate, and the volume usage amount of the solvent III is 50-100mL/g based on the mass of graphene; the mass ratio of the POSS-based quaternary ammonium salt ionic liquid to the graphene is 3-1: 1.
10. The preparation method of the graphene hybrid particle flame retardant according to claim 3, wherein the N-alkylamine is one of trimethylamine, triethylamine or tripropylamine, and the mass ratio of the active POSS to the N-alkylamine is 1: 2.
11. The method of claim 3, wherein the catalyst is sodium iodide or potassium iodide, and the ratio of the amounts of the active POSS to the catalyst is 1: 0.5.
12. The method of claim 3, wherein the ratio of the amounts of the POSS to the anionic salt is 1: 2.
13. The preparation method of the graphene hybrid particle flame retardant according to claim 3, wherein the solvent I is acetonitrile.
14. The preparation method of the graphene hybrid particle flame retardant according to claim 3, wherein the solvent II is water.
15. The preparation method of the graphene hybrid particle flame retardant according to claim 3, wherein the mass ratio of the POSS-based quaternary ammonium salt ionic liquid to the graphene is 2: 1.
16. Use of the graphene hybrid particle flame retardant of claim 1 as an additive in the preparation of polyolefin polymer flame retardants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711072812.7A CN107815116B (en) | 2017-11-03 | 2017-11-03 | Graphene hybrid particle flame retardant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711072812.7A CN107815116B (en) | 2017-11-03 | 2017-11-03 | Graphene hybrid particle flame retardant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107815116A CN107815116A (en) | 2018-03-20 |
| CN107815116B true CN107815116B (en) | 2020-11-06 |
Family
ID=61603676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711072812.7A Active CN107815116B (en) | 2017-11-03 | 2017-11-03 | Graphene hybrid particle flame retardant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107815116B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109913968B (en) * | 2019-03-14 | 2021-04-30 | 福建省银河服饰有限公司 | Antibacterial polypropylene fiber and preparation method thereof |
| CN109778335B (en) * | 2019-03-14 | 2021-04-13 | 福建省银河服饰有限公司 | Modified polypropylene fiber and preparation method thereof |
| CN114231011B (en) * | 2022-01-12 | 2023-06-30 | 深圳市光亚塑胶电子有限公司 | Preparation method of phenyl phosphine oxide-graphene-POSS (polyhedral oligomeric silsesquioxane) -coordinated flame-retardant polycarbonate material |
| CN114940800B (en) * | 2022-05-31 | 2023-07-21 | 宁波格亿达光缆科技有限公司 | Antistatic high-flame-retardance PVC (polyvinyl chloride) optical cable material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443247A (en) * | 2011-09-16 | 2012-05-09 | 桂林理工大学 | Preparation method of graphene oxide grafted POSS (polyhedral oligomeric silsesquioxane) modified epoxy resin |
| CN103588808A (en) * | 2013-11-08 | 2014-02-19 | 复旦大学 | Polyhedral oligomeric silsesquioxane (POSS)-based solid ionic liquid, and preparation method and application thereof |
| CN104829863A (en) * | 2015-03-31 | 2015-08-12 | 台州学院 | Nanometer polyhedral oligomeric silsesquioxane fire retardant containing ionic liquid, and preparation method and application thereof |
| CN107236273A (en) * | 2017-06-19 | 2017-10-10 | 魏科峰 | A kind of PC/ABS plastic alloys of halogen-free flameproof and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120035309A1 (en) * | 2010-08-06 | 2012-02-09 | Baker Hughes Incorporated | Method to disperse nanoparticles into elastomer and articles produced therefrom |
-
2017
- 2017-11-03 CN CN201711072812.7A patent/CN107815116B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443247A (en) * | 2011-09-16 | 2012-05-09 | 桂林理工大学 | Preparation method of graphene oxide grafted POSS (polyhedral oligomeric silsesquioxane) modified epoxy resin |
| CN103588808A (en) * | 2013-11-08 | 2014-02-19 | 复旦大学 | Polyhedral oligomeric silsesquioxane (POSS)-based solid ionic liquid, and preparation method and application thereof |
| CN104829863A (en) * | 2015-03-31 | 2015-08-12 | 台州学院 | Nanometer polyhedral oligomeric silsesquioxane fire retardant containing ionic liquid, and preparation method and application thereof |
| CN107236273A (en) * | 2017-06-19 | 2017-10-10 | 魏科峰 | A kind of PC/ABS plastic alloys of halogen-free flameproof and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "simultaneous reduction and surface functionalization of graphene oxide with POSS for reducing fire hazards in epoxy composites";Xin Wang et al;《Journal of Materials Chemistry》;20121204;第22卷;第22037–22043页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107815116A (en) | 2018-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107815116B (en) | Graphene hybrid particle flame retardant and preparation method and application thereof | |
| CN102963898B (en) | Preparation method of dual-functional group organically modified montmorillonite | |
| CN104829863B (en) | A kind of nanoscale cage modle polysilsesquioxane fire retardant containing ionic liquid and its preparation method and application | |
| CN111072973B (en) | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant | |
| CN103289125B (en) | Phosphorus-nitrogen-silicon containing organic and inorganic hybrid fire retardant and preparation method thereof and formed polymer | |
| CN103435728B (en) | Porous gathers the preparation method of quaternary phosphonium type ionic liquid | |
| CN109180952B (en) | Nitrogen-phosphorus-silicon synergistic halogen-free flame retardant grafted with graphene and preparation method thereof | |
| CN103044463A (en) | Method for high-efficiency preparing zeolite imidazole metal organic frame ZIF-90 | |
| CN103374032B (en) | Ion liquid of quaternaries of a kind of organic phosphine functionalization and preparation method thereof | |
| CN109438488A (en) | A kind of preparation method of liquid Lithium bis (oxalate) borate salt | |
| Wang et al. | Energetic multi-component molecular solids of tetrafluoroterephthalic acid with some aza compounds by strong hydrogen bonds and weak intermolecular interactions of C–H⋯ F and C–H⋯ O | |
| CN104558046B (en) | A kind of hyperbranched ionic liquid based on hexachlorocyclotriph,sphazene and the application as fire retardant thereof | |
| CN105860595A (en) | Hyperbranched-polytriazole-functionalized graphene and preparation method thereof | |
| CN103396459A (en) | Method for preparing phosphorus silicate hybridization flame retardant from organic silicon waste liquid | |
| CN102924749B (en) | Ionic liquid-type phosphate fire retardant and preparation method thereof | |
| CN106905352A (en) | A kind of copper organic inorganic hybridization compound and its synthetic method | |
| CN106865526A (en) | β graphite alkenes and its synthetic method and the application in energy storage field | |
| CN103374033A (en) | Functionalized quaternary phosphonium salt ionic liquid of organic phosphine and preparation method thereof | |
| CN108409591B (en) | Star-shaped carboxylic acid group zwitterionic compound and preparation method and application thereof | |
| CN103374034B (en) | Pyridine ionic liquid of a kind of organic phosphine functionalization and preparation method thereof | |
| CN113277504A (en) | Multifunctional auxiliary agent containing graphene nano material and preparation method thereof | |
| CN105801867B (en) | A kind of expansion type flame retardant and preparation method thereof based on biomass structure | |
| CN107828056B (en) | POSS (polyhedral oligomeric silsesquioxane) based quaternary ammonium salt ionic liquid and preparation method thereof | |
| CN104117392A (en) | Supported catalyst and preparation method thereof | |
| CN102351796A (en) | Production process of imidazole ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231124 Address after: B205, No.179 Chezhan Road, Liushi Town, Leqing City, Wenzhou City, Zhejiang Province, 325600 Patentee after: Zhipu Qiwang (Wenzhou) Electric Power Technology Research Institute Co.,Ltd. Address before: Taizhou University, 1139 Shifu Avenue, Taizhou City, Zhejiang Province, 317000 Patentee before: TAIZHOU University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231215 Address after: 325600 Sulu micro business park, Liushi Town, Yueqing City, Wenzhou City, Zhejiang Province Patentee after: ZHEJIANG SUOTAI ELECTRIC CO.,LTD. Address before: B205, No.179 Chezhan Road, Liushi Town, Leqing City, Wenzhou City, Zhejiang Province, 325600 Patentee before: Zhipu Qiwang (Wenzhou) Electric Power Technology Research Institute Co.,Ltd. |
|
| TR01 | Transfer of patent right |