CN116082754B - Modified graphene oxide/hydrotalcite composite material, preparation method thereof and application thereof in flame-retardant reinforced polypropylene composite material - Google Patents
Modified graphene oxide/hydrotalcite composite material, preparation method thereof and application thereof in flame-retardant reinforced polypropylene composite material Download PDFInfo
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- CN116082754B CN116082754B CN202310000384.6A CN202310000384A CN116082754B CN 116082754 B CN116082754 B CN 116082754B CN 202310000384 A CN202310000384 A CN 202310000384A CN 116082754 B CN116082754 B CN 116082754B
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- 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 title claims abstract description 77
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 77
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 69
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 65
- -1 polypropylene Polymers 0.000 title claims abstract description 45
- 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 29
- 239000003063 flame retardant Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 37
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- 229910021389 graphene Inorganic materials 0.000 claims description 20
- 239000002893 slag Substances 0.000 claims description 18
- 229950000244 sulfanilic acid Drugs 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000012954 diazonium Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 150000001989 diazonium salts Chemical class 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 235000021355 Stearic acid Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000008117 stearic acid Substances 0.000 claims description 9
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000010344 sodium nitrate Nutrition 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 8
- 238000006193 diazotization reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012744 reinforcing agent Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000003440 toxic substance Substances 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08L23/14—Copolymers of propene
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a modified graphene oxide/hydrotalcite composite material, a preparation method thereof and application thereof in flame-retardant reinforced polypropylene composite material. Compared with the traditional PP material, the modified graphene oxide/hydrotalcite composite material can obviously improve the strength and flame retardance of the PP material under the condition of adding a small amount of reinforcing agent, has better mechanical property, expands the application range of the PP material, and has good dispersion effect in a PP system.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a modified graphene oxide/hydrotalcite composite material and a preparation method thereof, and a flame-retardant reinforced PP composite material prepared by adopting the modified graphene oxide/hydrotalcite composite material and a preparation method thereof.
Background
Polypropylene (PP) is a colorless, odorless, nontoxic, semitransparent thermoplastic synthetic resin with chemical resistance, heat resistance, and electrical insulation properties. Along with the development of the social and economic level and the progress of scientific technology, the limitation of the traditional reinforcing filler is increasingly apparent, and the exploration of novel environment-friendly functional filler becomes a hot spot.
Carbon black and the like are used for reinforcement in the traditional process of the plastic rubber material, but the material is difficult to greatly improve in performance due to the fact that the intermolecular force is strong, the specific surface area is large, agglomeration is easy to occur, and the dispersion is uneven in a plastic rubber matrix. The PP has the advantages that the flame retardant performance is improved by using a flame retardant additive, such as a halogen flame retardant, which is low in cost, good in processability and compatibility, and can be used for interrupting an exothermic process and inhibiting combustion by a free radical mechanism in a gas phase, but a large amount of toxic substances can be released in the combustion process; the metal hydroxide flame retardant is mainly aluminum hydroxide and magnesium hydroxide, utilizes endothermic decomposition to release steam to dilute a combustible polymer decomposition product, reduces the temperature of the polymer to be lower than the temperature required for maintaining combustion through endothermic decomposition, and promotes the formation of carbon through dehydration and cooling so as to isolate a base material from a heat source, thereby playing a flame retardant role. For example, CN201210077136.3 uses magnesium hydroxide as PP flame retardant, and in order to achieve good flame retardant effect, it is generally required to add more than 50%.
Disclosure of Invention
Aiming at the defects in the prior art, the invention firstly provides a modified graphene oxide/hydrotalcite composite material and a preparation method thereof, and the composite material can be used for preparing a PP composite material.
The invention also provides a flame-retardant reinforced polypropylene composite material and a preparation method thereof, the flame-retardant reinforced polypropylene composite material is prepared by adopting the modified graphene oxide/hydrotalcite composite material and synergistically acting with components such as ethylene-octene copolymer, compared with the traditional PP material, the flame-retardant reinforced polypropylene composite material can obviously improve the strength and flame retardance of the PP material under the condition of adding a small amount of reinforcing agent, has better mechanical property, expands the application range of the PP material, and has good dispersion effect in a PP system.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
The invention provides a modified graphene oxide/hydrotalcite composite material, which is prepared by the following steps:
1) Dissolving sulfanilic acid in NaOH aqueous solution, adding sodium nitrate, uniformly mixing, adding concentrated hydrochloric acid for diazotization reaction, and generating diazonium salt solution;
2) Adding graphene oxide into water, fully stirring and performing ultrasonic dispersion, and then adding the diazonium salt solution obtained in the step 1) into the water to react to obtain modified graphene oxide dispersion;
3) Placing the steel slag powder into a ball mill, adding absolute ethyl alcohol for ball milling, drying, adding the steel slag powder into a phosphoric acid aqueous solution for vigorous stirring, centrifuging to obtain supernatant, regulating the pH of the supernatant to 12-13 by NaOH, standing for crystallization, and filtering, washing and drying to obtain hydrotalcite;
4) Adding hydrotalcite obtained in the step 3) into water, vigorously stirring to enable the hydrotalcite to be fully swelled and scattered to prepare white slurry to obtain hydrotalcite emulsion, then adding the hydrotalcite emulsion into the modified graphene oxide dispersion liquid obtained in the step 2), reacting under stirring, and then filtering, washing and drying to obtain the modified graphene oxide/hydrotalcite composite material.
In the present invention, the concentration of the sulfanilic acid in the aqueous NaOH solution in the step 1) is 0.05 to 0.2g/ml, preferably 0.1 to 0.15g/ml;
the concentration of the aqueous NaOH solution is 5 to 20% by weight, preferably 5 to 10% by weight.
In the invention, the mass ratio of the sulfanilic acid to the sodium nitrate in the step 1) is 1:0.2-0.5, preferably 1:0.4-0.5.
In the invention, the mass ratio of the concentrated hydrochloric acid in the step 1) to the sulfanilic acid is 1, calculated by HCL contained in the concentrated hydrochloric acid: 0.5-2, preferably 1:1 to 1.5;
The concentration of the concentrated hydrochloric acid is 30-40wt%, preferably 36-38wt%.
In the invention, the diazotization reaction in the step 1) is carried out at the temperature of-2-5 ℃, preferably 0-2 ℃ for 20-60min, preferably 30-40min;
Preferably, the concentrated hydrochloric acid is continuously fed in the reaction process, preferably dropwise fed; the addition time is 5 to 20min, preferably 10 to 15min, which is counted in the reaction time.
In the present invention, the concentration of graphene oxide added to water in step 2) is 0.1 to 0.5wt%, preferably 0.2 to 0.3wt%.
In the present invention, the stirring and ultrasonic dispersion in step 2) is carried out for 20 to 60 minutes, preferably 30 to 40 minutes.
In the invention, the mass ratio of the graphene oxide in the step 2) to the sulfanilic acid in the step 1) is 1:1-5, preferably 1:3-5.
In the present invention, the reaction in step 2) is carried out at a temperature of-2 to 5 ℃, preferably 0 to 2 ℃, for a time of 2 to 5 hours, preferably 2 to 3 hours;
Preferably, the diazonium salt solution of step 1) is fed continuously during the reaction, preferably dropwise; the addition time is 5 to 20min, preferably 10 to 15min, which is counted in the reaction time.
In the invention, the grain size of the steel slag powder in the step 3) is 0.2-2mm, and preferably, the steel slag powder mainly comprises substances such as calcium oxide, silicon dioxide, aluminum oxide, magnesium oxide, iron oxide and the like, for example, anyang Yongxing steel of a sand steel group.
In the invention, the concentration of the absolute ethyl alcohol added into the steel slag powder in the step 3) is 0.1-0.5g/ml, preferably 0.1-0.2g/ml.
In the present invention, the ball milling time in step 3) is 4 to 12 hours, preferably 6 to 12 hours, and the particle size after ball milling is 0.1 to 1mm, preferably 0.1 to 0.5mm.
In the invention, the concentration of the steel slag powder added into the phosphoric acid aqueous solution in the step 3) is 0.01-0.1g/ml, preferably 0.05-0.1g/ml;
the concentration of the phosphoric acid aqueous solution is 10 to 30wt%, preferably 15 to 20wt%.
In the invention, the stirring speed of the intense stirring in the step 3) is 200-1000r/min, preferably 300-500r/min; the temperature is 70-100deg.C, preferably 80-85deg.C, and the time is 2-5 hr, preferably 2-3 hr.
In the present invention, the standing crystallization temperature in step 3) is 40-60 ℃, preferably 50-60 ℃, and the time is 8-16 hours, preferably 8-10 hours.
In the invention, the filtration, washing (water washing) and drying in the step 3) are conventional operations in the field, and the invention does not have specific requirements.
In the present invention, the hydrotalcite emulsion of step 4) has a hydrotalcite concentration of 1 to 5wt%, preferably 2 to 3wt%.
In the invention, the stirring speed of the intense stirring in the step 4) is 200-1000r/min, preferably 300-500r/min; the temperature is 85-100deg.C, preferably 85-90deg.C, and the time is 20-60min, preferably 30-40min.
In the invention, the mass ratio of the hydrotalcite emulsion in the step 4) to the modified graphene oxide dispersion liquid in the step 2) is 1:0.5-4, preferably 1:0.5-1.
In the present invention, the reaction in step 4) is carried out at a temperature of 85 to 100℃and preferably 85 to 90℃for a period of 2 to 6 hours and preferably 3 to 4 hours.
In the invention, the filtration, washing (water washing) and drying in the step 4) are conventional operations in the field, and the invention does not have specific requirements.
The invention also provides a flame-retardant reinforced polypropylene composite material, which comprises the following raw materials in parts by weight:
95-100 parts, preferably 95-96 parts, of polypropylene;
5-15 parts, preferably 5-10 parts, of ethylene-octene copolymer;
5-20 parts of modified graphene oxide/hydrotalcite composite material, preferably 5-15 parts;
2-5 parts, preferably 3-5 parts, of naphthenic oil;
0.5-2 parts, preferably 1-2 parts, of stearic acid;
1-5 parts, preferably 1.5-2 parts, of zinc stearate;
2-10 parts, preferably 3-5 parts, of zinc oxide;
1-5 parts of antioxidant, preferably 2-3 parts.
According to the invention, the polypropylene is selected from the group consisting of copolymerized polypropylene with a melt index of 3-100g/10min, preferably WH-EP548R product and WH-EP648V product;
According to the invention, the ethylene-octene copolymer is chosen from the group of Dow 8150. Ethylene-octene copolymer (POE) elastomers have a soft chain crimp structure of octene and a crystalline structure of ethylene chains. The POE has a relatively narrow molecular weight distribution, short and uniform branched chains, and thus has good processability, flowability, rebound resilience and excellent low-temperature properties. Has excellent comprehensive physical and mechanical properties and good processability.
According to the invention, the naphthenic oil is selected from the group consisting of caratekn 4010. According to the invention, POE, naphthenic oil and the like are added into the PP material matrix, so that the fluidity of the matrix is improved under the synergistic effect, the filler is well dispersed in the polymer matrix, the compatibility with PP is better, and the effect of modifying the filler is fully exerted.
The particle size of the zinc oxide is 0.1-0.2 mu m.
According to the present invention, the antioxidant is at least one selected from hindered phenols and phosphites, preferably a combination of the two, more preferably at least one selected from 2, 6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite.
The invention also discloses a preparation method of the flame-retardant reinforced polypropylene composite material, which comprises the following steps:
S1, putting polypropylene granules into a torque rheometer for mixing, then sequentially adding ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, antioxidant, naphthenic oil and modified graphene oxide/hydrotalcite composite material, and mixing for 20-30min;
S2, placing the mixture prepared in the step 1) for 24-32 hours, preparing a sheet with the thickness of 3-5mm by using a tablet press, cutting, and extruding and granulating by using a double-screw extruder to prepare the flame-retardant reinforced polypropylene composite material.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
According to the invention, sodium sulfanilate diazonium salt is used for grafting graphene oxide to prepare sulfonated graphene oxide, so that benzenesulfonate radicals are grafted on graphene oxide sheets, and then benzenesulfonate radical organic anion intercalated hydrotalcite is utilized to prepare the modified graphene oxide/hydrotalcite composite material. According to the invention, the graphene oxide and the hydrotalcite are compounded by utilizing the diazonium salt of the sulfanilic acid, so that the agglomeration phenomenon when the graphene oxide is independently used as a reinforcing agent is avoided. Meanwhile, the ethylene-octene copolymer and the naphthenic oil are added into the matrix, so that the fluidity of the matrix is improved under the synergistic effect of the ethylene-octene copolymer and the naphthenic oil, and the filler is well dispersed in the PP matrix.
Compared with the common PP composite material, the flame retardant reinforced PP composite material prepared by the invention has the advantages of enhancing the flame retardance of the material, providing better mechanical properties, expanding the application range of the material and providing a new idea for the functional PP composite material.
Drawings
FIG. 1 is a cross-sectional quenched microscopic morphology of a modified graphene oxide/hydrotalcite and PP blended material of example 3;
FIG. 2 is a cross-sectional quenched microscopic morphology graph of a modified graphene oxide/hydrotalcite and PP blended material of comparative example 2 without POE;
Fig. 3 is a graph of the cross-sectional quenched microscopic morphology of the unmodified graphene oxide/hydrotalcite and PP blend material of comparative example 3.
Detailed Description
The invention is further illustrated below in connection with specific examples, but the invention is not limited to these examples only.
In each example and comparative example of the present invention, the main raw materials were obtained by purchasing the following raw materials and reagents, all obtained by the common commercial route unless otherwise specified:
PP pellet: wanhua WH-EP648R;
ethylene-octene copolymer: a ceramic 8150;
naphthenic oil: kelamayKN 4010;
steel slag: the grain diameter is 0.2-2mm, and the sand steel group is Anyang Yongxing steel slag;
Graphene oxide: the preparation is carried out by adopting a modified Hummers method, and the steps are that 10g of expanded graphite is dissolved in 230ml of concentrated sulfuric acid, the uniform magnetic stirring state is kept, 30gKMnO g of graphite is slowly added, the reaction is carried out for 3 hours, and the temperature of the system is raised to 98 ℃. Then 400ml deionized water, 100ml 5wt% H2O2 hydrogen peroxide are added in sequence until the solution turns golden yellow without bubbles, and finally 200ml 5wt% HCl solution is added. And centrifuging and washing the suspension to be neutral, and freeze-drying to obtain graphene oxide.
The main performance in the embodiment of the invention is tested by the following method:
melt index: MI40 type melt index apparatus, temperature 230 ℃.
Tensile strength: CMT 6014 type universal testing machine with testing speed of 100mm min-1.
Rockwell hardness: GT-601-RSH Rockwell hardness tester.
Oxygen index: JF-3 type oxygen index analyzer, mixed gas flow rate 10 L.min-1, sample specification 100mm x 10mm x 3.2mm.
UL-94 test: CZF-3 vertical burner, sample size 125 mm. Times.10 mm. Times.3.2 mm.
Example 1
The preparation method of the modified graphene oxide/hydrotalcite composite material comprises the following steps:
1) 1g of sulfanilic acid is fully dissolved in 10ml of NaOH aqueous solution with the concentration of 5wt%, then 0.4g of sodium nitrate is added for uniform mixing, the mixture is moved to an ice-water bath with the temperature of 0 ℃, 3g of concentrated hydrochloric acid with the concentration of 37wt% is dripped in 10min for diazotization reaction for 30min, and diazonium salt solution is generated.
2) Dissolving 0.25g of graphene oxide in 100g of deionized water, fully stirring and ultrasonically dispersing for 30min, then dropwise adding diazonium salt solution into the solution within 10min, and carrying out ice bath reaction at 0 ℃ for 2h to obtain modified graphene oxide dispersion liquid.
3) Taking 20g of steel slag powder with the grain diameter of 0.5mm, ball milling for 12h by adding 150ml of absolute ethyl alcohol to the grain diameter of 0.1mm, drying, adding into 400ml of phosphoric acid aqueous solution with the concentration of 20wt%, vigorously stirring for 4h at the rotating speed of 400r/min and the temperature of 85 ℃, centrifuging to obtain supernatant, adjusting the pH value of the supernatant to be 13 by NaOH, standing and crystallizing for 16h at the temperature of 60 ℃, and carrying out suction filtration, washing and drying on the obtained precipitate to obtain hydrotalcite.
4) Adding 2.5g of hydrotalcite into 100g of deionized water, vigorously stirring for 30min at the rotation speed of 400r/min and the temperature of 90 ℃ to enable the hydrotalcite to be fully swelled and scattered to prepare white slurry to obtain hydrotalcite emulsion, then adding the hydrotalcite emulsion into 100g of modified graphene oxide dispersion liquid in the step 2), stirring and reacting for 4h at the temperature of 90 ℃, and carrying out suction filtration, washing and drying on the obtained precipitate to obtain the modified graphene oxide/hydrotalcite composite material.
The flame-retardant reinforced polypropylene composite material is prepared from the following raw materials in parts by weight:
95 parts of PP (WH-EP 548R), 10 parts of ethylene-octene copolymer (Dow 8150), 5 parts of the prepared modified graphene oxide/hydrotalcite composite material, 3 parts of naphthenic oil (Kramayi KN 4010), 1 part of stearic acid, 1.5 parts of zinc stearate, 5 parts of zinc oxide (particle size of 0.1 mu m), and 1 part of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
S1, putting PP granules into a torque rheometer for mixing, then sequentially adding ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, antioxidant, naphthenic oil and modified graphene oxide/hydrotalcite composite material, and mixing for 30min;
S2, placing the mixture prepared in the step 6) for 24 hours, preparing a sheet with the thickness of 3-5mm by using a tablet press, cutting, and then extruding and granulating by using a double-screw extruder to prepare the flame-retardant reinforced PP polypropylene composite material, wherein the performance test results are shown in Table 1.
Example 2
The preparation method of the modified graphene oxide/hydrotalcite composite material comprises the following steps:
1) 1g of sulfanilic acid is fully dissolved in 10ml of 5wt% NaOH aqueous solution, 0.45g of sodium nitrate is added to be uniformly mixed, the mixture is moved to a water bath with the temperature of 1 ℃, 3.5g of concentrated hydrochloric acid with the concentration of 37wt% is dripped in 10min for diazotization reaction for 35min, and diazonium salt solution is generated.
2) Dissolving 0.3g of graphene oxide in 100g of deionized water, fully stirring and ultrasonically dispersing for 30min, then dropwise adding diazonium salt solution into the solution within 10min, and carrying out ice bath reaction at 1 ℃ for 2.5h to obtain modified graphene oxide dispersion liquid.
3) Taking 20g of steel slag powder with the grain diameter of 0.5mm, ball milling for 10 hours by adding 150ml of absolute ethyl alcohol to the grain diameter of 0.1mm, drying, adding into 400ml of 17wt% phosphoric acid aqueous solution, vigorously stirring for 2 hours at the rotating speed of 300r/min and the temperature of 80 ℃, centrifuging to obtain supernatant, adjusting the pH value of the supernatant to be 13 by NaOH, standing and crystallizing for 10 hours at the temperature of 50 ℃, and carrying out suction filtration, washing and drying on the obtained precipitate to obtain hydrotalcite.
4) Adding 2g of hydrotalcite into 100g of deionized water, vigorously stirring for 30min at the speed of 300r/min and the temperature of 85 ℃ to enable the hydrotalcite to be fully swelled and scattered to prepare white slurry to obtain hydrotalcite emulsion, then adding the hydrotalcite emulsion into 90g of modified graphene oxide dispersion liquid in the step 2), stirring and reacting for 6h at the temperature of 85 ℃, and carrying out suction filtration, washing and drying on the obtained precipitate to obtain the modified graphene oxide/hydrotalcite composite material.
The flame-retardant reinforced polypropylene composite material is prepared from the following raw materials in parts by weight:
95 parts of PP (WH-EP 648V), 8 parts of ethylene-octene copolymer (Dow 8150), 10 parts of the prepared modified graphene oxide/hydrotalcite composite material, 4 parts of naphthenic oil (Kramayi KN 4010), 2 parts of stearic acid, 2 parts of zinc stearate, 5 parts of zinc oxide (particle size of 0.15 mu m) and 2 parts of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
The procedure was the same as in example 1, and the results of the performance test are shown in Table 1.
Example 3
The preparation method of the modified graphene oxide/hydrotalcite composite material comprises the following steps:
1) 1g of sulfanilic acid is fully dissolved in 10ml of 5wt% NaOH aqueous solution, then 0.5g of sodium nitrate is added for uniform mixing, the mixture is moved to a water bath with the temperature of 2 ℃, and 4g of 37wt% concentrated hydrochloric acid is dripped in 10min for diazotization reaction for 40min, so as to generate diazonium salt solution.
2) Dissolving 0.3g of graphene oxide in 100g of deionized water, fully stirring and ultrasonically dispersing for 30min, then dropwise adding diazonium salt solution into the solution within 10min, and carrying out ice bath reaction at 2 ℃ for 3h to obtain modified graphene oxide dispersion liquid.
3) Taking 20g of steel slag powder with the grain diameter of 0.5mm, ball milling for 6 hours by adding 150ml of absolute ethyl alcohol to the grain diameter of 0.1mm, drying, adding into 400ml of 15wt% phosphoric acid aqueous solution, vigorously stirring for 3 hours at the rotating speed of 500r/min and the temperature of 85 ℃, centrifuging to obtain supernatant, adjusting the pH value of the supernatant to be 13 by NaOH, standing and crystallizing for 8 hours at the temperature of 60 ℃, and carrying out suction filtration, washing and drying on the obtained precipitate to obtain hydrotalcite.
4) Adding 3g of hydrotalcite into 100g of deionized water, vigorously stirring for 35min at the rotation speed of 500r/min and the temperature of 90 ℃ to enable the hydrotalcite to be fully swelled and scattered to prepare white slurry to obtain hydrotalcite emulsion, then adding the hydrotalcite emulsion into 80g of modified graphene oxide dispersion liquid in the step 2), stirring and reacting for 5h at the temperature of 85 ℃, and carrying out suction filtration, washing and drying on the obtained precipitate to obtain the modified graphene oxide/hydrotalcite composite material.
The flame-retardant reinforced polypropylene composite material is prepared from the following raw materials in parts by weight:
95 parts of PP (WH-EP 548R), 8 parts of ethylene-octene copolymer (Dow 8150), 15 parts of the prepared modified graphene oxide/hydrotalcite composite material, 3 parts of naphthenic oil (Kramayi KN 4010), 1 part of stearic acid, 2 parts of zinc stearate, 5 parts of zinc oxide (particle size of 0.2 mu m) and 2 parts of antioxidant 2, 6-di-tert-butyl-4-methylphenol.
The procedure was the same as in example 1, and the results of the performance test are shown in Table 1.
Comparative example 1
A polypropylene composite was prepared by the method of reference example 1, except that: the raw material formulation was not added with the modified graphene oxide/hydrotalcite composite material, and the other operations were the same as in example 1, to prepare a polypropylene composite material, and the performance test results are shown in table 1.
Comparative example 2
A polypropylene composite was prepared by the method of example 1, except that POE was not added to the raw material formulation, and the other operations were the same as in example 1, to prepare a polypropylene composite, and the performance test results are shown in Table 1.
Comparative example 3
The polypropylene composite material is prepared by referring to the method of the embodiment 1, except that the steps 1) and 2) are omitted in the preparation method of the modified graphene oxide/hydrotalcite composite material, namely, the graphene oxide is not modified and is directly used in the step 4), so that the graphene oxide/hydrotalcite composite material is prepared. This was then used instead to prepare the polypropylene composite in example 1.
Comparative example 4
The polypropylene composite material is prepared by the method of the reference example 1, except that the step 3) is omitted in the preparation method of the modified graphene oxide/hydrotalcite composite material, namely, the commercial common magnesium aluminum hydrotalcite is directly used in the step 4), so that the graphene oxide/hydrotalcite composite material is prepared. This was then used instead to prepare the polypropylene composite in example 1.
The PP composite materials obtained in examples 1 to 3 and comparative examples 1 to 4 were subjected to a performance comparison test, and the results are shown in Table 1.
TABLE 1 Performance test results
Claims (39)
1. The preparation method of the modified graphene oxide/hydrotalcite composite material is characterized by comprising the following steps of:
1) Dissolving sulfanilic acid in NaOH aqueous solution, adding sodium nitrate, uniformly mixing, adding concentrated hydrochloric acid for diazotization reaction, and generating diazonium salt solution;
2) Adding graphene oxide into water, fully stirring and performing ultrasonic dispersion, and then adding the diazonium salt solution obtained in the step 1) into the water to react to obtain modified graphene oxide dispersion;
3) Placing the steel slag powder into a ball mill, adding absolute ethyl alcohol for ball milling, drying, adding the steel slag powder into a phosphoric acid aqueous solution for vigorous stirring, centrifuging to obtain supernatant, regulating the pH of the supernatant to 12-13 by NaOH, standing for crystallization, and filtering, washing and drying to obtain hydrotalcite;
4) Adding hydrotalcite obtained in the step 3) into water, vigorously stirring to enable the hydrotalcite to be fully swelled and scattered to prepare white slurry to obtain hydrotalcite emulsion, then adding the hydrotalcite emulsion into the modified graphene oxide dispersion liquid obtained in the step 2), reacting under stirring, and then filtering, washing and drying to obtain the modified graphene oxide/hydrotalcite composite material.
2. The method according to claim 1, wherein the concentration of the sulfanilic acid in the aqueous NaOH solution in step 1) is 0.05 to 0.2g/ml;
The concentration of the NaOH aqueous solution is 5-20wt%;
The mass ratio of the sulfanilic acid to the sodium nitrate in the step 1) is 1:0.2-0.5;
the dosage of the concentrated hydrochloric acid in the step 1) is 1 in terms of the mass ratio of HCL contained in the concentrated hydrochloric acid to sulfanilic acid: 0.5-2;
the concentration of the concentrated hydrochloric acid is 30-40wt%;
the diazotization reaction in the step 1) is carried out at the temperature of-2 to 5 ℃ for 20 to 60 minutes.
3. The method according to claim 2, wherein the concentration of the sulfanilic acid in the aqueous NaOH solution is 0.1 to 0.15g/ml.
4. The method according to claim 2, wherein the concentration of the aqueous NaOH solution is 5-10wt%.
5. The preparation method according to claim 2, wherein the mass ratio of the sulfanilic acid to the sodium nitrate is 1:0.4-0.5.
6. The preparation method according to claim 2, wherein the mass ratio of the concentrated hydrochloric acid to sulfanilic acid based on HCL contained therein is 1:1-1.5.
7. The method of claim 2, wherein the concentrated hydrochloric acid has a concentration of 36-38wt%.
8. The method according to claim 2, wherein the diazotisation is carried out at a temperature of 0-2 ℃ for a time of 30-40min.
9. The process according to claim 2, wherein the concentrated hydrochloric acid is fed continuously during the diazotisation reaction for a period of time ranging from 5 to 20 minutes, said period being taken into account during the reaction.
10. The method of claim 9, wherein the addition time is 10-15 minutes.
11. The method according to claim 9, wherein the concentrated hydrochloric acid is added dropwise.
12. The method of claim 1, wherein the graphene oxide of step 2) is added to water at a concentration of 0.1-0.5wt%;
Step 2) stirring and ultrasonic dispersing are carried out for 20-60min;
the mass ratio of the graphene oxide in the step 2) to the sulfanilic acid in the step 1) is 1:1-5;
The reaction in the step 2) is carried out at the temperature of-2 to 5 ℃ for 2 to 5 hours.
13. The method of claim 12, wherein the graphene oxide is added to the water at a concentration of 0.2-0.3wt%.
14. The method of claim 12, wherein the stirring and ultrasonic dispersion is performed for a period of 30-40 minutes.
15. The preparation method according to claim 12, wherein the mass ratio of the graphene oxide to the sulfanilic acid in the step 1) is 1:3-5.
16. The method according to claim 12, wherein the reaction is carried out at a temperature of 0 to 2 ℃ for a time of 2 to 3 hours.
17. The process according to claim 12, wherein the diazonium salt solution of step 1) is fed continuously during the reaction for a period of time ranging from 5 to 20 minutes, said period being counted in the reaction time.
18. The method of claim 17, wherein the addition time is 10-15 minutes.
19. The method according to claim 17, wherein the diazonium salt solution of step 1) is added dropwise.
20. The method according to claim 1, wherein the steel slag powder in step 3) has a particle size of 0.2-2mm;
the concentration of the absolute ethyl alcohol added into the steel slag powder in the step 3) is 0.1-0.5g/ml;
Step 3), the ball milling time is 20-60min, and the particle size after ball milling is 0.1-1mm;
The concentration of the steel slag powder added into the phosphoric acid aqueous solution in the step 3) is 0.01-0.1g/ml;
The concentration of the phosphoric acid aqueous solution is 10-30wt%;
Step 3) stirring vigorously, wherein the stirring speed is 200-1000r/min; the temperature is 70-100 ℃ and the time is 2-5h;
and 3) standing and crystallizing at 40-60 ℃ for 8-16h.
21. The method according to claim 20, wherein the concentration of the steel slag powder added to the absolute ethanol is 0.1-0.2g/ml.
22. The method according to claim 20, wherein the ball milling time is 30 to 40min and the particle size after ball milling is 0.1 to 0.5mm.
23. The method according to claim 20, wherein the concentration of the steel slag powder added to the phosphoric acid aqueous solution is 0.05-0.1g/ml.
24. The method of claim 20, wherein the aqueous phosphoric acid solution has a concentration of 15-20wt%.
25. The method of claim 20, wherein the vigorous stirring is at a stirring speed of 300-500r/min; the temperature is 80-85 ℃ and the time is 2-3h.
26. The method according to claim 20, wherein the standing crystallization temperature is 50 to 60 ℃ for 8 to 10 hours.
27. The process according to claim 1, wherein the hydrotalcite emulsion of step 4) has a hydrotalcite concentration of 1 to 5wt%;
Step 4) the stirring speed of the intense stirring is 200-1000r/min; the temperature is 85-100deg.C, and the time is 20-60min;
the mass ratio of the hydrotalcite emulsion in the step 4) to the modified graphene oxide dispersion liquid in the step 2) is 1:0.5-4;
the reaction in the step 4) is carried out at the temperature of 85-100 ℃ for 2-6h.
28. The process according to claim 27, wherein the hydrotalcite emulsion has a hydrotalcite concentration ranging from 2 to 3% by weight.
29. The method of claim 27, wherein the vigorous stirring rotation speed is 300-500r/min; the temperature is 85-90deg.C, and the time is 30-40min.
30. The preparation method according to claim 27, wherein the mass ratio of the hydrotalcite emulsion to the modified graphene oxide dispersion of step 2) is 1:1-2.
31. The method of claim 27, wherein the reaction is carried out at a temperature of 85-90 ℃ for a period of 3-4 hours.
32. A modified graphene oxide/hydrotalcite composite material prepared by the preparation method according to any one of claims 1 to 31.
33. Use of the modified graphene oxide/hydrotalcite composite material prepared by the preparation method according to any one of claims 1 to 31 in polypropylene composite material.
34. The flame-retardant reinforced polypropylene composite material is characterized by comprising the following raw materials in parts by weight:
95-100 parts of polypropylene;
5-15 parts of ethylene-octene copolymer;
5-20 parts of modified graphene oxide/hydrotalcite composite material;
2-5 parts of naphthenic oil;
0.5-2 parts of stearic acid;
1-5 parts of zinc stearate;
2-10 parts of zinc oxide;
1-5 parts of an antioxidant;
wherein the modified graphene oxide/hydrotalcite composite material is selected from the modified graphene oxide/hydrotalcite composite materials prepared by the preparation method according to any one of claims 1 to 31.
35. The flame retardant reinforced polypropylene composite according to claim 34, wherein the raw materials comprise, in parts by weight:
95-96 parts of polypropylene;
5-10 parts of ethylene-octene copolymer;
5-15 parts of modified graphene oxide/hydrotalcite composite material;
3-5 parts of naphthenic oil;
1-2 parts of stearic acid;
1.5-2 parts of zinc stearate;
3-5 parts of zinc oxide;
2-3 parts of antioxidant.
36. The flame retardant reinforced polypropylene composite material according to claim 34, wherein said polypropylene is selected from the group consisting of copolymerized polypropylene having a melt index of 3-100g/10 min;
The ethylene-octene copolymer is selected from the group consisting of dow 8150;
The naphthenic oil is selected from the group consisting of carateikn 4010;
the particle size of the zinc oxide is 0.1-0.2 mu m;
The antioxidant is at least one selected from hindered phenols and phosphites.
37. The flame retardant reinforced polypropylene composite of claim 36, wherein said polypropylene is selected from the group consisting of WH-EP548R, WH-EP648V.
38. The flame retardant reinforced polypropylene composite according to claim 36, wherein said antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite, 2, 6-di-tert-butyl-4-methylphenol.
39. A method of preparing a flame retardant reinforced polypropylene composite according to any one of claims 34 to 38, comprising the steps of:
S1, putting polypropylene granules into a torque rheometer for mixing, then sequentially adding ethylene-octene copolymer, stearic acid, zinc stearate, zinc oxide, antioxidant, naphthenic oil and modified graphene oxide/hydrotalcite composite material, and mixing for 20-30min;
S2, placing the mixture prepared in the step 1) for 24-32 hours, preparing a sheet with the thickness of 3-5mm by using a tablet press, cutting, and extruding and granulating by using a double-screw extruder to prepare the flame-retardant reinforced polypropylene composite material.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012013680A1 (en) * | 2010-07-28 | 2012-02-02 | Bayer Technology Services Gmbh | Electrically conductive pastes having increased charge storage capacity, comprising graphite layers and layers of laminar silicates or laminar double hydroxides, and electrical capacitors produced by means of said pastes |
| CN102666691A (en) * | 2009-10-15 | 2012-09-12 | 拜尔技术服务有限责任公司 | Composite materials having graphene layers and production and use thereof |
| CN104495833A (en) * | 2015-01-14 | 2015-04-08 | 北京化工大学 | Three-dimensional structure sulfur-nitrogen codope hierarchical pore graphene and preparation method thereof |
| CN106046683A (en) * | 2016-07-07 | 2016-10-26 | 西华大学 | Low-smoke flame-retardant polymer composite material and preparation method thereof |
| CN108774306A (en) * | 2018-06-29 | 2018-11-09 | 南京红宝丽新材料有限公司 | A kind of homogeneous non-inflammable polyurethane foam heat-insulating thermal insulation material and preparation method thereof |
| CN108863997A (en) * | 2018-06-22 | 2018-11-23 | 枣庄九星生物科技有限公司 | A kind of preparation method of 5 methyl furfural |
| CN111004434A (en) * | 2019-12-25 | 2020-04-14 | 福州大学 | High-wear-resistance anti-slip EVA (ethylene-vinyl acetate) composite foam material and preparation method thereof |
| CN111218065A (en) * | 2020-03-25 | 2020-06-02 | 叶丹平 | High-toughness flame-retardant polypropylene composite material |
| CN111995015A (en) * | 2020-07-07 | 2020-11-27 | 广西夏阳环保科技有限公司 | Composite heavy metal wastewater treatment agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2776506B1 (en) * | 2011-11-08 | 2019-12-25 | SABIC Global Technologies B.V. | High heat polycarbonate and siloxane copolycarbonate blends that provide ductile high heat options for flame retardant applications |
-
2023
- 2023-01-03 CN CN202310000384.6A patent/CN116082754B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666691A (en) * | 2009-10-15 | 2012-09-12 | 拜尔技术服务有限责任公司 | Composite materials having graphene layers and production and use thereof |
| WO2012013680A1 (en) * | 2010-07-28 | 2012-02-02 | Bayer Technology Services Gmbh | Electrically conductive pastes having increased charge storage capacity, comprising graphite layers and layers of laminar silicates or laminar double hydroxides, and electrical capacitors produced by means of said pastes |
| CN104495833A (en) * | 2015-01-14 | 2015-04-08 | 北京化工大学 | Three-dimensional structure sulfur-nitrogen codope hierarchical pore graphene and preparation method thereof |
| CN106046683A (en) * | 2016-07-07 | 2016-10-26 | 西华大学 | Low-smoke flame-retardant polymer composite material and preparation method thereof |
| CN108863997A (en) * | 2018-06-22 | 2018-11-23 | 枣庄九星生物科技有限公司 | A kind of preparation method of 5 methyl furfural |
| CN108774306A (en) * | 2018-06-29 | 2018-11-09 | 南京红宝丽新材料有限公司 | A kind of homogeneous non-inflammable polyurethane foam heat-insulating thermal insulation material and preparation method thereof |
| CN111004434A (en) * | 2019-12-25 | 2020-04-14 | 福州大学 | High-wear-resistance anti-slip EVA (ethylene-vinyl acetate) composite foam material and preparation method thereof |
| CN111218065A (en) * | 2020-03-25 | 2020-06-02 | 叶丹平 | High-toughness flame-retardant polypropylene composite material |
| CN111995015A (en) * | 2020-07-07 | 2020-11-27 | 广西夏阳环保科技有限公司 | Composite heavy metal wastewater treatment agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯的制备和改性及其与聚合物复合的研究进展;谢普 等;《材料导报》;20101130;第24卷;第163-166页 * |
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