CN103275408A - Graphene/layered double hydroxide composite flame retardant and preparation method of polystyrene nanometer flame-retardant composite material - Google Patents
Graphene/layered double hydroxide composite flame retardant and preparation method of polystyrene nanometer flame-retardant composite material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
Abstract
The invention relates to a graphene/layered double hydroxide composite flame retardant and a preparation method of a polystyrene nanometer flame-retardant composite material. The preparation method comprises the following steps of: dissolving a carbon nanotube into graphene oxide colloid; stirring and performing ultrasonic dispersion until the materials are dispersed uniformly; adding M<2+> salt and Al<3+> salt; adding urea; performing a reflux reaction to obtain a graphene/carbon nanotube/layered double hydroxide composite assembling body; mixing the composite assembling body and polystyrene resin; and performing melt extrusion to obtain the polystyrene nanometer flame-retardant composite material. The graphene/carbon nanotube/layered double hydroxide composite assembling body is prepared by dispersing carbon nanotubes by a graphene oxide nanosheet, controlling the pH value of the solution by the urea and reducing the graphene oxide into the graphene. The polystyrene nanometer flame-retardant composite material prepared by the melt extrusion method has excellent flame resistance and mechanical properties.
Description
Technical field
The present invention relates to a kind of preparation method of Halogen composite nanometer flame retardant, belong to the preparation of inorganic composite flame retardants and the technical field of application.
Background technology
Polystyrene is one of five big general-purpose plastics, and its goods are widely used among the every profession and trades such as electrical equipment, decoration, building, traffic, military project.Yet polystyrene is very easy to burning, and the fusion drippage is serious and discharge a large amount of black smokes in the combustion processes, therefore be necessary very much to its carry out fire-retardant, press down the security that cigarette handles to improve its application.Because the fire-retardant material of halogenated flame retardant can produce poisonous, mordant smog in a large number when burning, environment, mould are had pollution, corrosive nature.Based on the requirement of environment protection and Sustainable development, halogen-free flame-retardant system will have vast potential for future development.The halogen-free flame retardants system that is usually used in polymkeric substance mainly comprises phosphorus system, nitrogen system, silicon system, metal hydroxides etc., and nanoparticle forms the flame retardant properties that nano composite material can improve polymkeric substance if can be scattered in well in the polymeric matrix.Halogen nano composite fire retardant demonstrates the tempting prospect as flame-proofed polymer material, more is that the people favors reducing the hot release performance of material and satisfying in the environmental requirement particularly.
Graphene is a kind of carbonaceous novel material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline structure, have such as lower production cost, high-specific surface area, good mechanical performance and superior advantages such as conductivity, these superior characteristic make this novel material of Graphene demonstrate tempting application prospect (Shi Y in the flame retardant area of polymkeric substance, Li LJ. Chemically modified graphene:flame retardant or fuel for combustion J. Mater. Chem. 2011,21:3277-3279.).Very easily reunite between the graphene film sheet in Graphene/polymer nanocomposites, this is unfavorable for its fire-retardant to polymkeric substance.Layered double-hydroxide (LDH) is to pile up the compound that forms by interlayer anion and positively charged laminate, and its chemical constitution can be expressed as [M
2+ 1-xM
3+ x(OH)
2] (A
N-)
X/nMH
2O, wherein M
2+The expression divalent metal is as Mg
2+, Zn
2+, Cu
2+, Ni
2+Deng; M
3+Be trivalent metal cation, as Al
3+, Cr
3+, Fe
3+, Ga
3+Deng; A
N-For the tradable negatively charged ion of interlayer, as Cl
-, NO
3 -, CO
3 2-, OH
-, SO
4 2-Deng; X=M
3+/ (M
2++ M
3+) the ratio of amount of substance, in 0.2 ~ 0.33 scope, can obtain pure LDH usually, m is middle water molecule number.The metal ion that exists in the LDH synusia is the active principle that eliminates smoke; Product after the decomposition is alkaline porous mass, and specific surface is big, can adsorb particularly sour gas of obnoxious flavour.Thereby LDH can be as the fire-retardant and smoke suppressant of polymkeric substance.Yet inorganic combustion inhibitor needs bigger loading level just can reach desirable flame retardant effect usually, but the caused processing of big addition and product mechanical property extremely descend the degradation problem all to compare seriously.Therefore the low loading level of exploitation and the little composite efficient fire retardant of material mechanical performance influence had important practical significance and scientific research is worth.
Propose to utilize the method for electrochemistry and Hydrothermal Preparation Graphene/nickel aluminium LDH matrix material among patent CN20110425506.3 and the CN201110425497.8, prepared matrix material is mainly used in electrode material for super capacitor; Adopt hydrothermal method (Wang Z, Zhang X, Wang JH, Zou L, Liu ZT, Hao ZP. Preparation and capacitance properties of graphene/NiAl layered double-hydroxide nanocomposite. Journal of Colloid and Interface Science, 2013,396:251-257.), coprecipitation method (Li MX, Zhu JE, Zhang LL, Chen X, Zhang HM, Zhagn FZ, Xu SL, Evans DG. Facile synthesis of NiAl-layered double hydroxide/graphene hybrid with enhanced electrochemical properties for detection of dopamine. Nanoscale, 2011; 3:4240-4246.) Graphene/(cobalt aluminium, nickel aluminium) LDH matrix material of preparation can be used for electrode material for super capacitor and detect Dopamine HCL etc.So far, yet there are no Graphene/LDH matrix material as the report of fire retardant, and, adopt the matrix material of method for preparing still to exist and yield poorly, shortcomings such as graphene nano lamella, the reunion of LDH lamella, this is unfavorable for the performance of its flame retarding efficiency in polymer materials.
Summary of the invention
At the problems referred to above, technical problem to be solved by this invention is to seek a kind of polystyrene fire retardant, satisfy simultaneously halide-free smokeless, burning do not produce toxic gas, addition little, the mechanical property of material is influenced purposes such as less.
In order to address the above problem, the invention provides a kind of Graphene/layered double-hydroxide Halogen composite nanometer flame retardant, (CNTs) introduces the accumulation that suppresses graphene film between two-dimentional graphene film in advance with the one dimension carbon nanotube, utilizes Graphene, carbon nanotube, layered double-hydroxide to come the cooperative flame retardant polymer materials.
The technical solution adopted in the present invention is:
The preparation method of a kind of Graphene/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material may further comprise the steps:
1. compound concentration is graphene oxide (GO) colloid of 0.05-1g/L, after the one dimension carbon CNTs adding with acidifying mixture is carried out ultra-sonic dispersion 2-12h under condition of ice bath, obtains the colloidal dispersion of light/dark balance; The mass ratio of GO and CNTs is 1:1-1:20.
2. with M
2+Salt and Al
3+Salt (mol ratio is 2:1) successively adds the GO/CNTs colloidal dispersion that step (1) obtains, and adds urea (urea and Al after continuing to stir 10-30min
3+The mol ratio of salt is 10:1-20:1), mixing solutions behind 80-100 ℃ of following backflow 24h, with suspension cooling and with distilled water and ethanol repetitive scrubbing, then in 60 ℃ of vacuum drying ovens dry 24h to prepare GO/CNTs/LDH composite assembled.Described M is Mg, Zn, Co, Ni, any among the Ca.
3. with the composite assembled 1-10 part of GO/CNTs/LDH, the homogenizer mixing is used in 100 parts of mixing of polystyrene, obtains raw mix, and raw mix is melt extruded moulding through twin screw extruder, obtains the pipe/polyhenylethylene nano flame-proof composite material.
The processing parameter of described twin screw extruder is, length-to-diameter ratio is 20, and screw diameter is 40mm, and screw speed is 200-220rpm; Barrel temperature is 180-200 ℃, and head temperature is 190-200 ℃, and extruder temperature is 180-190 ℃.
Positively effect of the present invention is as follows:
1, the one dimension carbon nanotube is introduced in advance GO colloid for preparing Graphene/CNTs/LDH assembly and can be played the effect that stops graphene film and LDH sheet sheet to be reunited, play the fire-retardant effect of synergistic simultaneously.
2, composite assembled the comparing with halogen flame of the present invention's preparation reduced the secondary harm to environment, thereby reached requirements of green environmental protection.
3, the composite assembled formed lamella of the present invention's preparation and the splicing structure of one-dimensional nano line have represented the flame retarding efficiency height when fire retardant polystyrene, and addition is little, have the effect that presses down cigarette simultaneously, and less to the mechanical property influence of matrix material.
Description of drawings
Table 1 has provided the mechanical property of pure polystyrene resin and each embodiment matrix material, by table as seen, compare with polystyrene resin, the tensile strength of matrix material, shock strength change little, illustrate that the adding of Graphene/layered double-hydroxide composite fire retardant is less to the mechanical property influence of matrix material.
Fig. 1 is the SEM figure of the embodiment of the invention 1 preparation polystyrene nano composite material, and as seen from Figure 1, there is not agglomeration (magnification is 5000 times) significantly in the compact layer homogeneous that distributes in the polystyrene matrix in the polystyrene nano composite material.
Fig. 2 is the XRD figure of the polystyrene nano composite material of the embodiment of the invention 1 preparation, as seen from Figure 2, matrix material is compared the charateristic avsorption band that LDH and Graphene do not occur with polystyrene, illustrate that nanometer sheet peels off in matrix material, forms exfoliated polystyrene nano composite material.
Fig. 3 is the polystyrene nano composite material of embodiment 1 preparation and the heat release rate curve of pure polystyrene, as seen from Figure 3, compare with pure polystyrene, it is about 45% that the peak heat release rate of polystyrene nano composite material descends, and the flame retardant properties of matrix material obviously improves.
Fig. 4 is the polystyrene nano composite material of embodiment 1 preparation and the living cigarette rate curve of pure polystyrene, as seen from Figure 4, compare with pure polystyrene, the living cigarette speed of polystyrene nano composite material has obvious decline, wherein the peak is given birth to cigarette speed and is descended approximately 25%, and matrix material shows as good smoke suppressing effect.
Fig. 5 is the photo after the polystyrene nano composite material of the embodiment of the invention 1 preparation burns, and left side figure is polystyrene, and right figure is polystyrene nano composite material, as seen from the figure, almost burnouts after the polystyrene burning, does not have resistates; The resistates showed increased is compared with polystyrene in polystyrene nano composite material burning back, and composite assembled played excellent protection polystyrene matrix and fire-retardant effect are described.
Embodiment
Below by specific embodiment foregoing of the present invention is described in further detail.But this should be interpreted as that content of the present invention only limits to following example.
Embodiment 1
The preparation method of a kind of Graphene/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material, step is as follows:
(1) (preparation method is referring to Hummers W S for the GO colloid of preparation 1L 0.05g/L, Offeman R E. Preparation of graphite oxide. J Am Chem Soc, 1958,80:1339), with 0.2g CNTs(available from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences) (souring method is referring to Han YQ after the acidifying, Shen MX, Lin XC, Ding B, Zhang LJ, Tong H, Zhang XG. Ternary phase interfacial polymerization of polypyrrole/MWCNT nanocomposites with core-shell structure. Synthetic Metals, 2012,162:753-758.) add, mixture is carried out ultra-sonic dispersion 2h under condition of ice bath, obtain the colloidal dispersion of light/dark balance.
(2) with 0.2 mol MgCl
2(available from Nanjing Chemistry Reagent Co., Ltd.) and 0.1molAlCl
3(available from company limited of Nanjing Chemistry Reagent Co., Ltd.) successively adds in the GO/CNTs dispersion liquid that step (1) obtains, the urea that adds 1mol behind the lasting 10min of stirring, mixing solutions is behind 80-100 ℃ of following backflow 24h, with suspension cooling and with distilled water and ethanol repetitive scrubbing, then in 60 ℃ of vacuum drying ovens dry 24h to prepare GO/CNTs/LDH composite assembled.
(3) with composite assembled 5 parts of GO/CNTs/LDH, general purpose polystyrene resin (PG-383, available from Taiwan Qimei Industry Co., Ltd.) 100 parts of mixing, use the homogenizer mixing, obtain raw mix, raw mix is melt extruded moulding through twin screw extruder, obtain the pipe/polyhenylethylene nano flame-proof composite material.The processing parameter of twin screw extruder is that length-to-diameter ratio is 20, and screw diameter is 40mm, and screw speed is 200-220rpm, and barrel temperature is 180-200 ℃, and head temperature is 190-200 ℃, and extruder temperature is 180-190 ℃.
The preparation method of 2 one kinds of Graphenes of embodiment/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material, its place different with embodiment 1 is that the concentration of GO colloid becomes 0.1g/L, the quality of CNTs becomes 1g, and ultra-sonic dispersion 2h becomes 6h; MgCl in the step 2
2Become ZnCl
2Composite assembledly in the step 3 become 2 parts by 5 parts.
The preparation method of 3. 1 kinds of Graphenes of embodiment/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material, its place different with embodiment 1 is that the volume of GO colloid in the step 1 becomes 4L by 1L, the quality of CNTs becomes 4g, ultra-sonic dispersion 2h becomes 12h, composite assembledly in the step 3 becomes 1 part by 5 parts.
The preparation method of 4. 1 kinds of Graphenes of embodiment/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material, its place different with embodiment 1 is MgCl in the step 2
2Mole number become and to become 0.5mol by 0.2mol, MgCl
2Become CoCl
2, AlCl
3Mole number become 0.25mol by 0.1mol, the mole number of urea becomes 3mol by 1mol, composite assembledly in the step 3 becomes 8 parts by 5 parts.
The preparation method of 5. 1 kinds of Graphenes of embodiment/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material, its place different with embodiment 1 is that the volume of GO colloid in the step 1 becomes 5L by 1L, the quality of CNTs becomes 1.5g by 0.2g, and ultra-sonic dispersion 2h becomes 12h.MgCl in the step 2
2Mole number become 1mol by 0.2mol, MgCl
2Become NiCl
2, AlCl
3Mole number become 0.5mol by 0.1mol, the mole number of urea becomes 10mol by 1mol, composite assembledly in the step 3 becomes 1 part by 5 parts.
The preparation method of 6. 1 kinds of Graphenes of embodiment/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material, its place different with embodiment 1 is that the volume of GO colloid in the step 1 becomes 2L by 1L, and the quality of CNTs becomes 0.1g by 0.2g.MgCl in the step 2
2Mole number become 0.4mol by 0.2mol, MgCl
2Become CaCl
2, AlCl
3Mole number become 0.2mol by 0.1mol, the mole number of urea becomes 2mol by 1mol, composite assembledly in the step 3 becomes 10 parts by 5 parts.
The composite flame-proof material that embodiment 2-6 obtains shows after after testing: the composite material nanometer sheet for preparing is peeled off in matrix material, forms exfoliated polystyrene nano composite material; And there is not agglomeration significantly in the compact layer homogeneous that distributes in the polystyrene matrix in the polystyrene nano composite material; Compare with pure polystyrene, the living cigarette speed of polystyrene nano composite material has obvious decline, and wherein the about 25-50% of cigarette speed decline is given birth at the peak, and matrix material shows as good smoke suppressing effect, and flame retardant properties obviously improves; And the resistates showed increased is compared with polystyrene in polystyrene nano composite material burning back, and composite assembled played excellent protection polystyrene matrix and fire-retardant effect are described.
The mechanical property of the pure polystyrene resin of table 1 and each embodiment matrix material
| Material | Tensile strength (MPa) | Socle girder notched Izod impact strength (KJ/m2) |
| Pure polystyrene | 18.5 | 1.2 |
| Embodiment 1 | 20.5 | 1.3 |
| Embodiment 2 | 19.5 | 1.5 |
| Embodiment 3 | 18.8 | 1.6 |
| Embodiment 4 | 17.8 | 1.0 |
| Embodiment 5 | 21.2 | 1.8 |
| Embodiment 6 | 18.2 | 0.9 |
Claims (5)
1. the preparation method of Graphene/layered double-hydroxide composite fire retardant and pipe/polyhenylethylene nano flame-proof composite material is characterized in that step is as follows:
(1) carbon nanotube of acidifying is added in the graphene oxide colloid, stir, under condition of ice bath the ultrasonic colloidal dispersion that obtains black, standby;
(2) with M
2+Salt and Al
3+Salt successively is added in step (1) the gained colloidal dispersion, adding urea stirs, after mixing solutions refluxes, with gained suspension cooling and to prepare Graphene/carbon nanotube/layered double-hydroxide with distilled water and ethanol repetitive scrubbing, drying composite assembled, standby;
(3) composite assembled in the step (2) mixed with polystyrene resin, use the homogenizer mixing, obtain raw mix, raw mix is melt extruded moulding through twin screw extruder, obtain the pipe/polyhenylethylene nano composite flame-proof material.
2. according to the preparation method of the described Graphene of claim 1/layered double-hydroxide composite fire retardant, the concentration that it is characterized in that graphene oxide colloid in the step (1) is 0.05-1g/L, the mass ratio of the carbon nanotube of graphene oxide and acidifying is 1:1-1:20, and the ultra-sonic dispersion time is 2-12h.
3. according to the preparation method of the described Graphene of claim 1/layered double-hydroxide composite fire retardant, it is characterized in that the M described in the step (2)
2+Be Mg, Zn, Co, Ni, any among the Ca, M
2+Salt and Al
3+The mol ratio of salt is 2:1, urea and Al
3+The mol ratio of salt is 10:1-20:1, and the mixing solutions return time is 24h.
4. according to the preparation method of the described Graphene of claim 1/layered double-hydroxide composite fire retardant, it is characterized in that mass fraction composite assembled in the step (3) is 1-10 part, the mass fraction of polystyrene resin is 100 parts.
5. according to the preparation method of the described Graphene of claim 1/layered double-hydroxide composite fire retardant, the processing parameter that it is characterized in that the twin screw extruder described in the step (3) is, length-to-diameter ratio is 20, and screw diameter is 40mm, and screw speed is 200-220rpm; Barrel temperature is 180-200 ℃, and head temperature is 190-200 ℃, and extruder temperature is 180-190 ℃.
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| CN109082017A (en) * | 2018-07-11 | 2018-12-25 | 河南科技大学 | A kind of phosphorus doping carbon nanotube/organically-modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
| CN109082017B (en) * | 2018-07-11 | 2020-11-20 | 河南科技大学 | Phosphorus-doped carbon nanotube/organic modified layered double hydroxide/polyolefin flame-retardant material and preparation method thereof |
| CN109399629A (en) * | 2018-12-28 | 2019-03-01 | 北京航空航天大学 | A kind of preparation method of the sol solutions containing two-dimensional nano container payload corrosion inhibiter |
| CN110421776A (en) * | 2019-08-29 | 2019-11-08 | 西华大学 | A kind of multiple dimensioned stratiform fire proofing and preparation method thereof |
| CN110421776B (en) * | 2019-08-29 | 2022-02-15 | 西华大学 | Multi-scale layered flame-retardant material and preparation method thereof |
| CN113980551A (en) * | 2021-11-15 | 2022-01-28 | 西南石油大学 | Hydrotalcite-based water-based epoxy resin intumescent fire-retardant coating |
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