CN106046683A - Low-smoke flame-retardant polymer composite material and preparation method thereof - Google Patents

Low-smoke flame-retardant polymer composite material and preparation method thereof Download PDF

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CN106046683A
CN106046683A CN201610530036.XA CN201610530036A CN106046683A CN 106046683 A CN106046683 A CN 106046683A CN 201610530036 A CN201610530036 A CN 201610530036A CN 106046683 A CN106046683 A CN 106046683A
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graphene oxide
flame retardant
smoke
polymer composite
low
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CN106046683B (en
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陈明军
李欣儡
王许
刘治国
钟柳
罗蔓
钟怡娟
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Xihua University
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract

The invention belongs to the field of polymer materials and relates to a low-smoke flame-retardant polymer composite material. The low-smoke flame-retardant polymer composite material is prepared from, by weight, 100 parts of a polymer matrix, 10-60 parts of an intumescent flame retardant, 0-30 parts of a charring agent, 0-20 parts of a foaming agent and 0.5-5 parts of a smoke inhibition synergist, wherein the smoke inhibition synergist is a hybrid formed by loading of metal ions on the surface of graphene oxide. The hybrid formed by loading of the metal ions on the surface of graphene oxide is used as the smoke inhibition synergist which is synergically used with the the intumescent flame retardant to improve flame retardation and smoke inhibition performances of various polymer materials such as epoxy resin and polyurethane. A new approach is provided for preparation of multifunctional high-performance polymer composite materials.

Description

Low-smoke and flame retardant polymer composite and preparation method thereof
Technical field
The present invention relates to a kind of low-smoke and flame retardant polymer composite, belong to polymeric material field.
Background technology
Along with development in science and technology, constantly guide and promote that the progress of new material, monistic material matrix are progressively combined Material is substituted.Multifunctional composite becomes research focus, and fire-retardant and smoke-inhibiting type composite is i.e. one of them direction.
At present, on the basis of considering flame-retardant smoke inhibition efficiency and environmental conservation, many selection phosphorus flame retardants are to high score Sub-matrix material carries out flame-retarded modification.Phosphorus flame retardant has higher flame retarding efficiency, is not likely to produce poison gas.Near Year, the phosphorus flame retardant such as phosphate ester, phosphite ester, organophosphorated salt emerges in an endless stream.
It addition, along with the understanding intensification to fire hazard, and the reinforcement of environmental consciousness, it is fire-retardant that smoke suppressing becomes evaluation The important indicator of material.Time in early days to material flame-retardant smoke inhibition modification, improve Flame Retardancy energy, with self-extinguishment with often rising everything on one attempt Avoid flue gas to produce, but when really running into big fire, this effect is actually difficulty with.And fire retardant is made with smoke suppressant For material additive, when making an addition in matrix, higher addition can have negative effect to composite materials property simultaneously.By This, clay pit species filler is shown one's talent, and it is the most cheap, and have special nanostructured and flame-retarding metal from Son composition, therefore can be used for the fire-retardant of polymeric material and enhancing modified.
Layered double hydroxide (being called for short LDH) is made up of two or more metal ion, has brucite The mixed metal hydroxides of layered crystal structure.In prior art, LDH is similar to as the application of flame-retardant additive more Mentality of designing disclosed in CN101544815A, use surfactant to LDH body organic modification, then with other fire retardant Cooperate and make an addition in matrix；(Feng Tao, LDHs base height presses down structure control and the performance of cigarette halogen-free inorganic nano-meter flame retardants to document Research, Beijing University of Chemical Technology) report utilizes phosphate radical intercalation LDH, and the flame-retardant smoke inhibition being used for PE is modified.
But, prior art not yet has in the polymer material system with fire retardant, introduces area load metal ion Hybrid as pressing down, cigarette synergist and expansion type flame retardant are collaborative to be used, to improve the fire-retardant performance of composite and smoke suppressing Relevant report.
Summary of the invention
The present invention using the hybrid of surface of graphene oxide loaded metal ion as pressing down cigarette synergist and expansion type flame-retarding Agent is collaborative to be used, with the fire-retardant and smoke suppressing of the multiple macromolecular material such as reinforced epoxy and polyurethane；For preparing many merits New way can be provided by high performance polymer composite.
Technical scheme:
First technical problem that the invention solves the problems that is to provide a kind of low-smoke and flame retardant polymer composite, its raw material bag Include:
Polymeric matrix 100 weight portion, expansion type flame retardant 10～60 weight portion, carbon forming agent 0～30 weight portion, foaming agent 0～20 weight portions, press down cigarette synergist 0.5～5 weight portion；Wherein, pressing down cigarette synergist described in is surface of graphene oxide gold-supported Belong to the hybrid of ion.
In the present invention, in described hybrid metal be the form with metal cation with the oxygen of surface of graphene oxide bear from Sub-key is closed, and metal ion is dispersed on graphene oxide lamella.
Further, pressing down the load capacity of metal ion in cigarette synergist described in is 0.7～4%.
Further, the temperature pressing down weightless 5% correspondence of cigarette synergist described in is 180～280 DEG C.
Further, described polymeric matrix is epoxy resin, polyurethane, polyethylene, polypropylene, polystyrene or polychlorostyrene second At least one in alkene.
Further, described expansion type flame retardant is APP, melamine polyphosphate, melamine phosphate, phosphorus At least one in acid ammonium magnesium, Firebrake ZB, phosphate ester or expansible graphite.
Further, described carbon forming agent is tetramethylolmethane, starch, sorbitol, mannitol, phenolic resin, epoxy resin, poly-ammonia At least one in ester or triazines carbon forming agent.
Further, described foaming agent is tripolycyanamide, dicyandiamide, APP, melamine polyphosphate, tripolycyanamide At least one in phosphate, ammonium borate, dicyandiamide formaldehyde resin, Lauxite or polyamide.
Further, pressing down cigarette synergist described in uses ion exchange by metal ion uniform load to graphene oxide table Face.
Above-mentioned ion exchange comprises the steps:
1) graphite oxide and deionized water are prepared finely dispersed graphene oxide under sonic oscillation and release effect Suspension, wherein, the concentration of graphene oxide suspension is: 0.0005～0.005g/mL；
2) by metering, slaine is added in graphene oxide suspension, under sonic oscillation and release effect, prepare dispersion Uniform mixed liquor；
3) finally by step 2) gained mixed liquor stir at 30～60 DEG C to solution ph stablize constant (ion exchange thorough , solution ph no longer changes at the end, and about 7), through filtering, washing, it is dried the hydridization preparing graphene oxide-loaded metal ion Thing.
Described slaine be Schweinfurt green, cobaltous acetate, nickel acetate, palladium, ferric nitrate, copper nitrate, cobalt nitrate, nickel nitrate, Palladous nitrate. or platinum nitrate.
Described graphite oxide is 1:0.5～3 with the mass ratio of slaine.
Further, the preparation method of described hybrid comprises the following steps:
(1) adding in reactor by graphite oxide, deionized water, dropping weak base regulation solution ph is 7～8, ultrasonic Graphite oxide is peeled off, it is thus achieved that graphene oxide suspension under vibration and microwave heating；
(2) by metering, slaine is added in graphene oxide suspension, continue to shell under sonic oscillation and microwave heating Can stop obtaining mixed liquor after stable to suspension concentration；During whole, regulate pH with weak base, control pH=7～8；
(3) after stripping terminates, being proceeded to by mixed liquor in other reactors, control temperature, at 30～60 DEG C, stirs 8～24h, After stirring terminates, filter, after washing at least 3 times (preferably 3～6 times), then be washed till few 3 times (preferably 3～6 with organic solvent Secondary), under 50～70 DEG C (preferably 60 DEG C), then it is vacuum dried 8～16h (preferably 12h), prepares graphene oxide-loaded The hybrid of metal ion.
In step (1) and (2), described microwave heating temperature is 30～80 DEG C.
In step (1) and (2), described weak base is ammonia, dimethylamine, triethylamine, aniline or pyridine；It is preferably ammonia.
In step (3), described organic solvent is acetone, chloroform, ethanol or ethyl acetate.
Second technical problem that the invention solves the problems that is to provide the preparation side of a kind of low-smoke and flame retardant polymer composite Method:
When polymeric matrix is thermosetting plastics, and described method is: by polymer monomer, expansion type flame retardant, carbon forming agent, Foaming agent is blended with pressing down cigarette synergist, and cured reaction prepares low-smoke and flame retardant polymer composite；
When polymeric matrix is thermoplastic, and described method is: by polymeric matrix, expansion type flame retardant, carbon forming agent, Foaming agent and press down cigarette synergist and prepare low-smoke and flame retardant polymer composite by the method that blended melting is mixing.
In the present invention, material preparation method is not particularly limited, utilizes published conventional preparation method to prepare.
Beneficial effects of the present invention:
The present invention by the hybrid of graphene oxide-loaded metal ion (in gained hybrid of the present invention metal cation with The negative oxygen ion of surface of graphene oxide combines, and has the effect being similar to metal-oxide) compound with expansion type flame retardant, use In the fire-retardant of reinforced polymeric material with during smoke suppressing, this hybrid shows following advantage:
First, metal cation is combined to have with the negative oxygen ion of surface of graphene oxide and is similar to urging of metal-oxide Change effect, can be dehydrated into charcoal by catalytic polymer, can be catalyzed again some poisonous gas (such as CO and HCN) in oxidation flue gas, from And reduce the release of toxicity flue gas.
Second, due to the specific surface area that graphene oxide is bigger, graphite oxide can be stoped at its area load metal ion Alkene reunion in polymeric matrix, contributes to this hybrid the most dispersed.
3rd, this hybrid can be worked in coordination with expanding fire retardant and be used to strengthen the compactness of layer of charcoal.
4th, graphene oxide has physics in the polymer and becomes carbon flame-proof effect, contributes to hindering polymer to decompose and produces Raw escaping gas is diffused into flame region, thus improves anti-flammability and reduce flue gas release.
It addition, in the present invention, the preparation of the hybrid of surface of graphene oxide loaded metal ion, raw material is easy to get, synthesis Method is simple, can use as synergist and expansion type flame retardant are collaborative, with the multiple material such as reinforced epoxy and polyurethane Fire-retardant and smoke suppressing；New way is provided for preparing multifunctional high-performance polymer composite.
Accompanying drawing explanation
Fig. 1 is graphite oxide, graphene oxide and graphene oxide-loaded copper ion hybrid (embodiment 1 gained hydridization Thing) thermal weight loss correlation curve figure.
Fig. 2 is the microscopic appearance figure (transmission electron microscope picture) of the graphene oxide-loaded copper ion hybrid of embodiment 1 preparation. From Fig. 2 (a) and (b), Cu2+Successfully load on graphene oxide lamella, and with Cu2+The form of group is dispersed in oxygen On functionalized graphene lamella.According to Fig. 2 (c), the lattice fringe in figure is analyzed by DigitalMicrograph software, The spacing of lattice tested out is about 0.22nm, and contrast standard card, with Cu2+Spacing of lattice consistent；And then confirm the present invention's Really prepare graphene oxide-loaded copper ion hybrid.
Fig. 3 is the epoxy composite material HRR pair adding and being not added with graphene oxide-loaded copper ion hybrid Compare curve chart.
Fig. 4 is the epoxy composite material cigarette rate of release pair adding and being not added with graphene oxide-loaded copper ion hybrid Compare curve chart
Fig. 5 is the epoxy composite material carbon monoxide release adding and being not added with graphene oxide-loaded copper ion hybrid RATES's curve chart.
Fig. 6 is the principle schematic that ion-exchange process of the present invention prepares GO loaded metal ion.
Detailed description of the invention
The present invention provides a kind of low-smoke and flame retardant polymer composite, and its raw material includes:
Polymeric matrix 100 weight portion, expansion type flame retardant 10～60 weight portion, carbon forming agent 0～30 weight portion, foaming agent 0～20 weight portions, press down cigarette synergist 0.5～5 weight portion；Wherein, pressing down cigarette synergist described in is surface of graphene oxide gold-supported Belong to the hybrid of ion.
In the present invention, in described hybrid metal be the form with metal cation with the oxygen of surface of graphene oxide bear from Sub-key is closed, and metal ion is dispersed on graphene oxide lamella.
In the present invention, expandable flame retardant can form foamed char, due to the iris action of layer of charcoal, not only has contribution to fire-retardant, Also there is contribution to pressing down cigarette, add that hybrid can increase charcoal amount, strengthen layer of charcoal compactness, and catalysis oxidation reduces flue gas toxity, It is thus possible to play synergism with expanding fire retardant, improve the flame retarding and smoke suppressing properties of material further.
Further, pressing down cigarette synergist described in uses ion exchange by metal ion uniform load to graphene oxide table Face.
Further, described in press down cigarette synergist under sonic oscillation and release effect, while peeling off, carry out ion friendship Change, thus metal ion is loaded to surface of graphene oxide.
Above-mentioned ion exchange comprises the steps:
1) graphite oxide and deionized water are prepared finely dispersed graphene oxide under sonic oscillation and release effect Suspension, wherein, the concentration of graphene oxide suspension is: 0.0005～0.005g/mL；
2) by metering, slaine is added in graphene oxide suspension, under sonic oscillation and release effect, prepare dispersion Uniform mixed liquor；
3) finally by step 2) gained mixed liquor stir at 30～60 DEG C to solution ph stablize constant (ion exchange thorough , solution ph no longer changes at the end, and about 7), through filtering, washing, it is dried the hydridization preparing graphene oxide-loaded metal ion Thing.
Further, the preparation method of described hybrid comprises the following steps:
(1) adding in reactor by graphite oxide, deionized water, dropping weak base regulation solution ph is 7～8, ultrasonic Graphite oxide is peeled off, it is thus achieved that graphene oxide suspension under vibration and microwave heating；
(2) by metering, slaine is added in graphene oxide suspension, continue to shell under sonic oscillation and microwave heating Can stop obtaining mixed liquor after stable to suspension concentration；During whole, regulate pH with weak base, control pH=7～8；
(3) after stripping terminates, being proceeded to by mixed liquor in other reactors, control temperature, at 30～60 DEG C, stirs 8～24h, After stirring terminates, filter, after washing at least 3 times (preferably 3～6 times), then be washed till few 3 times (preferably 3～6 with organic solvent Secondary), under 50～70 DEG C (preferably 60 DEG C), then it is vacuum dried 8～16h (preferably 12h), prepares graphene oxide-loaded The hybrid of metal ion.
In step (1) and (2), described weak base is ammonia, dimethylamine, triethylamine, aniline or pyridine；It is preferably ammonia.This In invention, the purpose using weak base to control pH=7～8 has two: first, and mild alkaline conditions beneficially graphite oxide is easier to be filled Divide and peel off；Second, while stripping, ammonium radical ion can first carry out ion exchange with hydrion, be conducive to next step with metal from Son carries out ion exchange；Because if metal ion is directly and hydrion carries out ion exchange, the hydrion exchanged can be given birth to Also acetic acid or nitric acid can be produced when becoming acetic acid or nitric acid, acetate or nitrate hydrolysis, unfavorable from the point of view of the angle chemically balanced Metal ion in acetate or nitrate ionizes out and carries out ion-exchange reactions, so that ion-exchanging efficiency is limited.
As a example by the graphene oxide hybrid preparing the load of positive bivalent metal ion, prepare graphene oxide-loaded metal The principle schematic of ion hybrid as shown in Figure 6, in step 1) in, graphite oxide (GY100) is stripped into graphene oxide While, the hydrion of surface of graphene oxide and ammonium radical ion carry out equal value exchange, it is thus achieved that loaded the oxidation of ammonium radical ion Graphene (GO)；In step 2) in, while more fully peeling off, metal ion and ammonium radical ion carry out equal value exchange, While obtaining graphene oxide-loaded metal ion hybrid, produce acetic acid ammonium salt by-product；In step 3) in, 30～60 Stir at DEG C to solution ph stablize constant time, ion exchange be properly completed.Through filtering, washing can remove by-product and miscellaneous Matter, the most just obtains graphene oxide-loaded metal ion hybrid.
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art will Understanding, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.In embodiment unreceipted specifically Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument unreceipted production firm person, be Can be by the commercially available conventional products bought and obtain.
The preparation of embodiment 1 graphene oxide-loaded metal ion hybrid
1g graphite oxide (GY100) and 200mL deionized water are added five mouthfuls of vials that ultrasonic-microwave linkage instrument is supporting In, dropping ammonia makes the pH value of solution 7～8, and at sonic oscillation, (ultrasonication amount is 200mL, changes different during sonic oscillation Width bar sends ultrasound wave when carrying out vibrating broken, and corresponding optimal crushing is certain, and this crushing is weighed with volume, Therefore, the crushing of horn and the volume of solution are identical)) and microwave heating (heating-up temperature 30 DEG C) effect lower to peel off 1.5 little Time, obtain the graphene oxide suspension that mass concentration is 0.0050g/mL；
Then in suspension, add 2g Schweinfurt green, continue to peel off under sonic oscillation and microwave heating must mix for 1 hour Liquid, in stripping process, measures the pH value of this mixed solution, if pH ＜ 7, then adds ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 60 DEG C in 500mL there-necked flask 12h, after stirring terminates, filters, Wash 5 times, then wash 3 times with acetone；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded copper ion miscellaneous Compound.Record copper ion load capacity 1.02% (load capacity refers to that copper ion quality accounts for the ratio of hybrid gross mass), weightlessness 5% Corresponding temperature is 230 DEG C.
In the present invention, the load capacity of copper ion uses inductively coupled plasma atomic emission test (ICP～AES) to obtain Arrive；Weightless temperature employing thermogravimetric analysis (TGA) corresponding to 5% carries out test and obtains.
The preparation of embodiment 2 graphene oxide-loaded metal ion hybrid
0.5g graphite oxide (GY100) and 300mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping ammonia makes the pH value of solution 7～8, (heats at sonic oscillation (ultrasonication amount is 300mL) and microwave heating Temperature 40 DEG C) act on lower stripping 1 hour, obtain the graphene oxide suspension that mass concentration is 0.0017g/mL；
Then in suspension, add 1.5g cobaltous acetate, continue to peel off under sonic oscillation and microwave heating must mix for 1 hour Close liquid, in stripping process, measure the pH value of this mixed solution, if pH ＜ 7, then add ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 50 DEG C in 500mL there-necked flask 9h, after stirring terminates, filters, Wash 5 times, then wash 4 times with ethanol；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded cobalt ion miscellaneous Compound.Recording cobalt ion load capacity 0.81%, temperature corresponding to weightless 5% is 210 DEG C.
The preparation of embodiment 3 graphene oxide-loaded metal ion hybrid
1.5g graphite oxide (GY100) and 400mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping triethylamine makes the pH value of solution 7～8, (adds at sonic oscillation (ultrasonication amount is 400mL) and microwave heating Hot temperature 40 DEG C) act on lower stripping 1 hour, obtain the graphene oxide suspension that mass concentration is 0.0037g/mL；
Then in suspension, add 1.5g nickel acetate, continue to peel off 0.5 hour under sonic oscillation and microwave heating Mixed liquor, in stripping process, measures the pH value of this mixed solution, if pH ＜ 7, then adds triethylamine until pH is 7～8；
Mixed solution stripping completed transfers to stir at 40 DEG C in 500mL there-necked flask 15h, after stirring terminates, filters, Wash 5 times, then wash 4 times with chloroform；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded nickel ion miscellaneous Compound.Recording nickel ion load capacity 0.70%, temperature corresponding to weightless 5% is 180 DEG C.
The preparation of embodiment 4 graphene oxide-loaded metal ion hybrid
2g graphite oxide (GY100) and 500mL deionized water are added five mouthfuls of vials that ultrasonic-microwave linkage instrument is supporting In, dropping aniline makes the pH value of solution 7～8, (heats temperature at sonic oscillation (ultrasonication amount is 500mL) and microwave heating Spend 50 DEG C) act on lower stripping 3 hours, obtain the graphene oxide suspension that mass concentration is 0.0040g/mL；
Then in suspension, add 1g palladium, continue to peel off under sonic oscillation and microwave heating must mix for 1.5 hours Close liquid, in stripping process, measure the pH value of this mixed solution, if pH ＜ 7, then add aniline until pH is 7～8；
Mixed solution stripping completed transfers to stir at 45 DEG C in 500mL there-necked flask 8h, after stirring terminates, filters, Wash 5 times, then wash 6 times with ethanol；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded palladium ion miscellaneous Compound.Recording palladium ion load capacity 4.00%, temperature corresponding to weightless 5% is 280 DEG C.
The preparation of embodiment 5 graphene oxide-loaded metal ion hybrid
0.2g graphite oxide (GY100) and 400mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping dimethylamine makes the pH value of solution 7～8, (adds at sonic oscillation (ultrasonication amount is 400mL) and microwave heating Hot temperature 80 DEG C) act on lower stripping 0.5 hour, obtain the graphene oxide suspension that mass concentration is 0.0005g/mL；
Then in suspension, add 0.4g ferric nitrate, continue to peel off under sonic oscillation and microwave heating must mix for 2 hours Close liquid, in stripping process, measure the pH value of this mixed solution, if pH ＜ 7, then add dimethylamine until pH is 7～8；
Mixed solution stripping completed transfers to stir at 30 DEG C in 500mL there-necked flask 24h, after stirring terminates, filters, Wash 5 times, then wash 5 times by ethyl acetate；Then, at 60 DEG C be vacuum dried 12 hours, prepare graphene oxide-loaded ferrum from Sub-hybrid.Recording iron ion load capacity 1.56%, temperature corresponding to weightless 5% is 206 DEG C.
The preparation of embodiment 6 graphene oxide-loaded metal ion hybrid
0.32g graphite oxide (GY100) and 350mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping ammonia makes the pH value of solution 7～8, (heats at sonic oscillation (ultrasonication amount is 350mL) and microwave heating Temperature 60 C) act on lower stripping 2 hours, obtain the graphene oxide suspension that mass concentration is 0.0009g/mL；
Then in suspension, add 0.7g copper nitrate, continue to peel off under sonic oscillation and microwave heating must mix for 1 hour Close liquid, in stripping process, measure the pH value of this mixed solution, if pH ＜ 7, then add ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 50 DEG C in 500mL there-necked flask 18h, after stirring terminates, filters, Wash 5 times, then wash 3 times with ethanol；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded copper ion miscellaneous Compound.Recording copper ion load capacity 1.48%, temperature corresponding to weightless 5% is 246 DEG C.
The preparation of embodiment 7 graphene oxide-loaded metal ion hybrid
1g graphite oxide (GY100) and 400mL deionized water are added five mouthfuls of vials that ultrasonic-microwave linkage instrument is supporting In, dropping ammonia makes the pH value of solution 7～8, (heats temperature at sonic oscillation (ultrasonication amount is 400mL) and microwave heating Spend 45 DEG C) act on lower stripping 2.5 hours, obtain the graphene oxide suspension that mass concentration is 0.0025g/mL；
Then in suspension, add 1.5g cobalt nitrate, continue to peel off under sonic oscillation and microwave heating must mix for 1 hour Close liquid, in stripping process, measure the pH value of this mixed solution, if pH ＜ 7, then add ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 35 DEG C in 500mL there-necked flask 10h, after stirring terminates, filters, Wash 5 times, then wash 4 times with acetone；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded cobalt ion miscellaneous Compound.Cobalt ion load capacity 0.95%, temperature corresponding to weightless 5% is 196 DEG C.
The preparation of embodiment 8 graphene oxide-loaded metal ion hybrid
0.8g graphite oxide (GY100) and 200mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping ammonia makes the pH value of solution 7～8, (heats at sonic oscillation (ultrasonication amount is 200mL) and microwave heating Temperature 70 C) act on lower stripping 1.5 hours, obtain the graphene oxide suspension that mass concentration is 0.0040g/mL；
Then in suspension, add 1.6g nickel nitrate, continue to peel off 1.5 hours under sonic oscillation and microwave heating Mixed liquor, in stripping process, measures the pH value of this mixed solution, if pH ＜ 7, then adds ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 55 DEG C in 500mL there-necked flask 12h, after stirring terminates, filters, Wash 5 times, then wash 3 times with chloroform；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded nickel ion miscellaneous Compound.Recording nickel ion load capacity 1.05%, temperature corresponding to weightless 5% is 216 DEG C.
The preparation of embodiment 9 graphene oxide-loaded metal ion hybrid
1.2g graphite oxide (GY100) and 300mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping ammonia makes the pH value of solution 7～8, (heats at sonic oscillation (ultrasonication amount is 300mL) and microwave heating Temperature 65 DEG C) act on lower stripping 1 hour, obtain the graphene oxide suspension that mass concentration is 0.0040g/mL；
Then in suspension, add 1g Palladous nitrate., continue to peel off under sonic oscillation and microwave heating must mix for 2 hours Liquid, in stripping process, measures the pH value of this mixed solution, if pH ＜ 7, then adds ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 40 DEG C in 500mL there-necked flask 20h, after stirring terminates, filters, Wash 5 times, then wash 5 times by ethyl acetate；Then, at 60 DEG C be vacuum dried 12 hours, prepare graphene oxide-loaded palladium from Sub-hybrid.Recording palladium ion load capacity 3.35%, temperature corresponding to weightless 5% is 266 DEG C.
The preparation of embodiment 10 graphene oxide-loaded metal ion hybrid
1.4g graphite oxide (GY100) and 400mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping ammonia makes the pH value of solution 7～8, (heats at sonic oscillation (ultrasonication amount is 400mL) and microwave heating Temperature 50 C) act on lower stripping 2.5 hours, obtain the graphene oxide suspension that mass concentration is 0.0035g/mL；
Then in suspension, add 0.8g platinum nitrate, continue to peel off under sonic oscillation and microwave heating must mix for 1 hour Close liquid, in stripping process, measure the pH value of this mixed solution, if pH ＜ 7, then add ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 40 DEG C in 500mL there-necked flask 20h, after stirring terminates, filters, Wash 5 times, then wash 6 times with acetone；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide-loaded platinum ion miscellaneous Compound.Recording platinum ion load capacity 2.47%, temperature corresponding to weightless 5% is 259 DEG C.
Comparative example
0.3g graphite oxide (GY100) and 200mL deionized water are added five mouthfuls of glass that ultrasonic-microwave linkage instrument is supporting In Ping, dropping ammonia makes the pH value of solution 7～8, (heats at sonic oscillation (ultrasonication amount is 200mL) and microwave heating Temperature 50 C) act on lower stripping 1 hour, obtain the graphene oxide suspension that mass concentration is 0.0015g/mL；
Then to suspension is continued under sonic oscillation and microwave heating peel off 1 hour mixed liquor, in stripping process, Measure the pH value of this mixed solution, if pH ＜ 7, then add ammonia until pH is 7～8；
Mixed solution stripping completed transfers to stir at 30 DEG C in 500mL there-necked flask 12h, after stirring terminates, filters, Wash 5 times, then wash 3 times with acetone；Then, it is vacuum dried 12 hours at 60 DEG C, prepares graphene oxide.Weightless 5% institute is right Answering temperature is 94 DEG C.
Graphite oxide, graphene oxide and graphene oxide-loaded copper ion hybrid (embodiment 1 gained hybrid) Thermal weight loss correlation curve figure is as shown in Figure 1.As shown in Figure 1, after stripping, the heat stability of graphene oxide improves (higher than oxidation Graphite), and after surface of graphene oxide has loaded copper ion, heat stability is improved greatly.Heat stability Raising, the most graphene oxide-loaded copper ion hybrid is applied to macromolecular material.
Embodiment 11
According to table 1 formula, respectively epoxy resin (containing firming agent), ammonium polyphosphate flame retardant (APP), graphene oxide are born Copper-loaded ion hybrid (Cu2+-GO), add in glass beaker by metering, (about 60 DEG C) are stirred for uniformly in a heated condition, Pouring mould the most while hot into be placed in baking oven solidifying to obtain flame-retardant high-molecular composite, solidification temperature is 120 DEG C, hardening time For 2h.
Embodiment 12～13
According to table 1 formula, use the method identical with embodiment 11, prepare flame-retardant high-molecular composite.
Comparative example 2
According to table 1 formula, use the method identical with embodiment 11, prepare fire retarding epoxide resin.
Comparative example 3
According to table 1 formula, use the method identical with embodiment 11, prepare the epoxy resin being not added with fire retardant.
Table 1 embodiment and the formula table of comparative example flame-retardant high-molecular composite
Note: APP ammonium polyphosphate flame retardant；MPP flame-retardants melamine Quadrafos；Cu2+～GO oxygen Functionalized graphene supported copper ion hybrid.In table/represent be not added with.
Fig. 3 is the epoxy composite material (embodiment 11～EP/18% adding graphene oxide-loaded copper ion hybrid APP/2%Cu2+～Go) and be not added with the epoxy composite material (comparative example 2～EP/ of graphene oxide-loaded copper ion hybrid 20%APP), the heat release of the pure epoxy resin (NeatEP) of fire retardant and graphene oxide-loaded copper ion hybrid it is not added with RATES's curve chart.From the figure 3, it may be seen that Cu2+～the addition of GO can reduce the HRR of the fire-retardant EP of APP further.
Fig. 4 is the epoxy composite material (embodiment 11～EP/18% adding graphene oxide-loaded copper ion hybrid APP/2%Cu2+～Go) and be not added with the epoxy composite material (comparative example 2～EP/ of graphene oxide-loaded copper ion hybrid 20%APP), the cigarette release of the pure epoxy resin (NeatEP) of fire retardant and graphene oxide-loaded copper ion hybrid it is not added with RATES's curve chart.As shown in Figure 4, Cu2+～the addition of GO can reduce the cigarette generating rate of the fire-retardant EP of APP further.
Fig. 5 is the epoxy composite material carbon monoxide release adding and being not added with graphene oxide-loaded copper ion hybrid RATES's curve chart.As shown in Figure 5, Cu2+～the addition of GO can reduce carbon monoxide (CO) generation of the fire-retardant EP of APP further Speed.
In summary, fire retarding epoxide resin adds graphene oxide-loaded metal ion hybrid, improve APP resistance Fire-retardant and the smoke suppressing of combustion epoxy resin, reduces the fire risk of epoxy resin.
The test result of embodiment 12 and embodiment 13 shows, it is fire-retardant compared to be not added with hybrid to the addition of hybrid Macromolecular material, HRR reduces by 26% and 37% respectively, and cigarette generating rate reduces by 18% and 24% respectively, carbon monoxide Generating rate reduces by 15% and 27% respectively.As can be seen here, expansion type flame-retardant polymer introduces graphene oxide-loaded gold Belong to ion hybrid, all can effectively reduce the HRR of polymer, cigarette generating rate and carbon monoxide generating rate.

Claims (10)

1. low-smoke and flame retardant polymer composite, it is characterised in that described composite raw material includes:
Polymeric matrix 100 weight portion, expansion type flame retardant 10～60 weight portion, carbon forming agent 0～30 weight portion, foaming agent 0～ 20 weight portions, press down cigarette synergist 0.5～5 weight portion；Wherein, press down described in cigarette synergist be surface of graphene oxide carried metal from The hybrid of son.
Low-smoke and flame retardant polymer composite the most according to claim 1, it is characterised in that described in press down metal in cigarette synergist The load capacity of ion is 0.7～4%.
Low-smoke and flame retardant polymer composite the most according to claim 1 or claim 2, it is characterised in that described in press down cigarette synergist lose The temperature weighing 5% correspondence is 180～280 DEG C.
4. according to low-smoke and flame retardant polymer composite described in any one of claims 1 to 3, it is characterised in that
Described polymeric matrix be in epoxy resin, polyurethane, polyethylene, polypropylene, polystyrene or polrvinyl chloride at least A kind of；Or:
Described expansion type flame retardant is APP, melamine polyphosphate, melamine phosphate, ammoniomagnesium phosphate, boric acid At least one in zinc, phosphate ester or expansible graphite；Or:
Described carbon forming agent is tetramethylolmethane, starch, sorbitol, mannitol, phenolic resin, epoxy resin, polyurethane or triazines At least one in carbon forming agent；Or:
Described foaming agent is tripolycyanamide, dicyandiamide, APP, melamine polyphosphate, melamine phosphate, boric acid At least one in ammonium, dicyandiamide formaldehyde resin, Lauxite or polyamide.
5. according to low-smoke and flame retardant polymer composite described in any one of Claims 1 to 4, it is characterised in that described in press down cigarette association Effect agent uses ion exchange by metal ion uniform load to surface of graphene oxide.
Low-smoke and flame retardant polymer composite the most according to claim 5, it is characterised in that described ion exchange include as Lower step:
1) graphite oxide and deionized water are prepared under sonic oscillation and release effect finely dispersed graphene oxide to suspend Liquid, wherein, the concentration of graphene oxide suspension is: 0.0005～0.005g/mL；
2) by metering ratio, slaine is added in graphene oxide suspension, under sonic oscillation and release effect, prepare dispersion all Even mixed liquor；
3) finally by step 2) gained mixed liquor stir at 30～60 DEG C stablize to solution ph constant, through filtering, washing, dry The dry hybrid preparing graphene oxide-loaded metal ion.
Low-smoke and flame retardant polymer composite the most according to claim 6, it is characterised in that described ion exchange include as Lower step:
(1) adding in reactor by graphite oxide, deionized water, dropping weak base regulation solution ph is 7～8, at sonic oscillation With stripping graphite oxide under microwave heating, it is thus achieved that graphene oxide suspension；
(2) by metering ratio, slaine is added in graphene oxide suspension, continue to peel off under sonic oscillation and microwave heating Can stop obtaining mixed liquor after stablizing to suspension concentration；During whole, it is 7～8 with weak base regulation pH；
(3) after stripping terminates, being proceeded to by mixed liquor in other reactors, control temperature, at 30～60 DEG C, stirs 8～24h, stirring After end, filter, after wash at least 3 times, then with organic solvent washing at least 3 times, then at 50～70 DEG C vacuum drying 8～ 16h, prepares the hybrid of graphene oxide-loaded metal ion.
8. according to low-smoke and flame retardant polymer composite described in claim 6 or 7, it is characterised in that
Described slaine is Schweinfurt green, cobaltous acetate, nickel acetate, palladium, ferric nitrate, copper nitrate, cobalt nitrate, nickel nitrate, nitric acid Palladium or platinum nitrate；Described graphite oxide is 1:0.5～3 with the mass ratio of slaine.
Low-smoke and flame retardant polymer composite the most according to claim 7, it is characterised in that
In step (1) and (2), described microwave heating temperature is 30～80 DEG C；Or:
In step (1) and (2), described weak base is ammonia, dimethylamine, triethylamine, aniline or pyridine；It is preferably ammonia；Or:
In step (3), described organic solvent is acetone, chloroform, ethanol or ethyl acetate.
10. the preparation method of low-smoke and flame retardant polymer composite described in any one of claim 1～9, described method is:
When polymeric matrix is thermosetting plastics, and described method is: by polymer monomer, expansion type flame retardant, carbon forming agent, foaming Agent and press down cigarette synergist be blended, cured reaction prepares low-smoke and flame retardant polymer composite；
When polymeric matrix is thermoplastic, and described method is: by polymeric matrix, expansion type flame retardant, carbon forming agent, foaming Agent and press down cigarette synergist and prepare low-smoke and flame retardant polymer composite by the method that blended melting is mixing.
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