CN106046683B - Low-smoke and flame retardant polymer composite and preparation method thereof - Google Patents
Low-smoke and flame retardant polymer composite and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of low-smoke and flame retardant polymer composite, belongs to polymeric material field.The present invention provides a kind of low-smoke and flame retardant polymer composite, and the composite material raw material includes：100 parts by weight of polymeric matrix, 10~60 parts by weight of expansion type flame retardant, 0~30 parts by weight of carbon forming agent, 0~20 parts by weight of foaming agent, 0.5~5 parts by weight of suppression cigarette synergist；Wherein, the suppression cigarette synergist is the hybrid of surface of graphene oxide loaded metal ion.Use is cooperateed with expansion type flame retardant by the present invention for the hybrid of surface of graphene oxide loaded metal ion, with the fire-retardant and smoke suppressing of a variety of high molecular materials such as reinforced epoxy and polyurethane；New way is provided to prepare multifunctional high-performance polymer composite.
Description
Technical field
The present invention relates to a kind of low-smoke and flame retardant polymer composite, belongs to polymeric material field.
Background technology
With development in science and technology, constantly guide and promote the progress of new material, monistic material matrix is progressively compound
Material is substituted.Multifunctional composite becomes research focus, and fire-retardant and smoke-inhibiting type composite material is one of direction.
At present, it is select phosphorus flame retardant to high score on the basis of flame-retardant smoke inhibition efficiency and environmental protection is considered more
Sub- basis material carries out flame-retarded modification.Phosphorus flame retardant has higher flame retarding efficiency, is not likely to produce poison gas.It is near
Year, the phosphorus flame retardant such as phosphate, phosphite ester, organophosphorated salt emerges in an endless stream.
In addition, 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.When being modified to material flame-retardant smoke inhibition early stage, Flame Retardancy energy is improved with often rising everything on one attempt, with self-extinguishment
To avoid flue gas from producing, but really when running into big fire, this effect is actually difficult to realize.And fire retardant and smoke suppressant are made
For material additive, while when making an addition in matrix, higher additive amount can have negative effect to composite materials property.By
This, clay pit species filler is shown one's talent, it is not only cheap, but also possess special nanostructured and flame-retarding metal from
Son composition, therefore be modified available for the fire-retardant of polymeric material and enhancing.
Layered double hydroxide (abbreviation LDH) is made of two or more metal ion, has hydrotalcite
The mixed metal hydroxides of layered crystal structure.In the prior art, it is similar to LDH as the application of flame-retardant additive more
Mentality of designing disclosed in CN101544815A, using surfactant to LDH body organic modifications, then with other fire retardants
Mutual cooperation is made an addition in matrix；Document (structure control of the high suppression cigarette halogen-free inorganic nano-meter flame retardants of Feng Tao, LDHs base and performance
Research, Beijing University of Chemical Technology) report utilizes phosphate radical intercalation LDH, and is modified for the flame-retardant smoke inhibition of PE.
But there has been no area load metal ion is introduced in the material system of polymer and fire retardant in the prior art
Hybrid as suppression cigarette synergist use is cooperateed with expansion type flame retardant, to improve the fire-retardant performance of composite material and smoke suppressing
Relevant report.
The content of the invention
The present invention is using the hybrid of surface of graphene oxide loaded metal ion as suppression cigarette synergist and expansion type flame-retarding
Agent collaboration uses, with the fire-retardant and smoke suppressing of a variety of high molecular materials such as reinforced epoxy and polyurethane；To prepare more work(
Energy high performance polymer composite material provides new way.
Technical scheme：
The invention solves first technical problem be to provide a kind of low-smoke and flame retardant polymer composite, its raw material bag
Include：
100 parts by weight of polymeric matrix, 10~60 parts by weight of expansion type flame retardant, 0~30 parts by weight of carbon forming agent, foaming agent
0~20 parts by weight, 0.5~5 parts by weight of suppression cigarette synergist；Wherein, the suppression cigarette synergist is surface of graphene oxide gold-supported
Belong to the hybrid of ion.
In the present invention, in the hybrid metal be in the form of metal cation and the oxygen of surface of graphene oxide bear from
Sub-key is closed, and metal ion is dispersed in graphene oxide layer.
Further, the load capacity of metal ion is 0.7~4% in the suppression cigarette synergist.
Further, the weightless 5% corresponding temperature of suppression cigarette synergist is 180~280 DEG C.
Further, the polymeric matrix is epoxy resin, polyurethane, polyethylene, polypropylene, polystyrene or polychlorostyrene second
At least one of alkene.
Further, the expansion type flame retardant is ammonium polyphosphate, melamine polyphosphate, melamine phosphate, phosphorus
At least one of sour ammonium magnesium, zinc borate, phosphate or expansible graphite.
Further, the carbon forming agent is pentaerythrite, starch, sorbierite, mannitol, phenolic resin, epoxy resin, poly- ammonia
At least one of ester or triazines carbon forming agent.
Further, the foaming agent is melamine, dicyandiamide, ammonium polyphosphate, melamine polyphosphate, melamine
At least one of phosphate, ammonium borate, dicyandiamide formaldehyde resin, Lauxite or polyamide.
Further, the suppression cigarette synergist uses ion-exchange by metal ion uniform load to graphene oxide table
Face.
Above-mentioned ion-exchange includes the following steps：
1) finely dispersed graphene oxide is made in graphite oxide and deionized water under sonic oscillation and release effect
Suspension, wherein, the concentration of graphene oxide suspension is：0.0005~0.005g/mL；
2) metal salt is added in graphene oxide suspension by metering, is made scattered under sonic oscillation and release effect
Uniform mixed liquor；
3) finally mixed liquor obtained by step 2) is stirred at 30~60 DEG C to solution ph and stablizes that constant (ion exchange is thorough
Behind bottom, solution ph no longer changes, about 7), filtered, washing, the dry hydridization that graphene oxide-loaded metal ion is made
Thing.
The metal salt for copper acetate, cobalt acetate, nickel acetate, palladium, ferric nitrate, copper nitrate, cobalt nitrate, nickel nitrate,
Palladium nitrate or platinum nitrate.
The mass ratio of the graphite oxide and metal salt is 1：0.5~3.
Further, the preparation method of the hybrid comprises the following steps：
(1) graphite oxide, deionized water are added in reactor, it is 7~8 that weak base, which is added dropwise, and adjusts solution ph, in ultrasound
Vibration and the lower stripping graphite oxide of microwave heating, obtain graphene oxide suspension；
(2) metal salt is added in graphene oxide suspension by metering, continues to shell under sonic oscillation and microwave heating
From can stop obtaining mixed liquor after to suspension concentration stablizing；In whole process, pH is adjusted with weak base, controls pH=7~8；
(3) after peeling off, mixed liquor is transferred in other reactors, control temperature stirs 8~24h at 30~60 DEG C,
After stirring, filtering, after washing at least 3 times (being preferably 3~6 times), then it (is preferably 3~6 to be washed till 3 times few with organic solvent
It is secondary), 8~16h (being preferably 12h) is then dried in vacuo under 50~70 DEG C (being preferably 60 DEG C), is made graphene oxide-loaded
The hybrid of metal ion.
In step (1) and (2), the microwave heating temperature is 30~80 DEG C.
In step (1) and (2), the weak base is ammonium hydroxide, dimethylamine, triethylamine, aniline or pyridine；Preferably ammonium hydroxide.
In step (3), the organic solvent is acetone, chloroform, ethanol or ethyl acetate.
The invention solves second technical problem be to provide a kind of preparation side of low-smoke and flame retardant polymer composite
Method：
When polymeric matrix is thermosetting plastics, the method is：By polymer monomer, expansion type flame retardant, carbon forming agent,
Low-smoke and flame retardant polymer composite is made in foaming agent and the synergist blending of suppression cigarette, cured reaction；
When polymeric matrix is thermoplastic, the method is：By polymeric matrix, expansion type flame retardant, carbon forming agent,
Low-smoke and flame retardant polymer composite is made by the method that blended melting is kneaded in foaming agent and suppression cigarette synergist.
In the present invention, material preparation method is not particularly limited, is made using published common preparation method.
Beneficial effects of the present invention：
The present invention by the hybrid of graphene oxide-loaded metal ion (in the present invention gained hybrid metal cation with
The negative oxygen ion of surface of graphene oxide combines, and has the function that to be similar to metal oxide) compounded with expansion type flame retardant, use
When the fire-retardant and smoke suppressing of reinforced polymeric material, which shows following advantage：
First, metal cation is combined with the negative oxygen ion of surface of graphene oxide with urging similar to metal oxide
Change acts on, can catalytic polymer be dehydrated into some poisonous gas (such as CO and HCN) in charcoal and catalysis oxidation flue gas, from
And reduce the release of toxicity flue gas.
Second, due to the specific surface area that graphene oxide is larger, graphite oxide can be prevented in its area load metal ion
The reunion of alkene in a polymer matrix, contributes to the hybrid dispersed in the base.
3rd, which can cooperate with expanding fire retardant using to strengthen the compactness of layer of charcoal.
4th, graphene oxide in the polymer there is physics to be acted on into carbon flame-proof, help to hinder polymer to decompose production
Raw escaping gas is diffused into flame region, so as to improve anti-flammability and reduce flue gas release.
In 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, use can be cooperateed with expansion type flame retardant as synergist, with multiple materials such as reinforced epoxy and polyurethane
Fire-retardant and smoke suppressing；New way is provided to prepare multifunctional high-performance polymer composite.
Brief description of the drawings
Fig. 1 is graphite oxide, graphene oxide and graphene oxide-loaded copper ion hybrid (1 gained hydridization of embodiment
Thing) thermal weight loss contrast curve.
Fig. 2 is the microscopic appearance figure (transmission electron microscope picture) of graphene oxide-loaded copper ion hybrid prepared by embodiment 1.
From Fig. 2 (a) and (b), Cu2+Successfully load in graphene oxide layer, and with Cu2+The form of group is dispersed in oxygen
On graphite alkene lamella.According to Fig. 2 (c), the lattice fringe in figure is analyzed by DigitalMicrograph softwares,
The spacing of lattice tested out is about 0.22nm, contrast standard card, with Cu2+Spacing of lattice it is consistent；And then confirm the present invention's
Graphene oxide-loaded copper ion hybrid really has been made.
Fig. 3 is addition and the epoxy composite material heat release rate pair for being not added with graphene oxide-loaded copper ion hybrid
Compare curve map.
Fig. 4 is addition and the epoxy composite material cigarette rate of release pair for being not added with graphene oxide-loaded copper ion hybrid
Compare curve map
Fig. 5 is addition and is not added with the epoxy composite material carbon monoxide release of graphene oxide-loaded copper ion hybrid
Rate comparison curve map.
Fig. 6 is the principle schematic that ion-exchange process of the present invention prepares GO loaded metal ions.
Embodiment
The present invention provides a kind of low-smoke and flame retardant polymer composite, its raw material includes：
100 parts by weight of polymeric matrix, 10~60 parts by weight of expansion type flame retardant, 0~30 parts by weight of carbon forming agent, foaming agent
0~20 parts by weight, 0.5~5 parts by weight of suppression cigarette synergist；Wherein, the suppression cigarette synergist is surface of graphene oxide gold-supported
Belong to the hybrid of ion.
In the present invention, in the hybrid metal be in the form of metal cation and the oxygen of surface of graphene oxide bear from
Sub-key is closed, and metal ion is dispersed in graphene oxide layer.
In the present invention, expandable flame retardant can form foamed char, due to the iris action of layer of charcoal, not only be contributed to fire-retardant,
Suppression cigarette is also contributed, can increase charcoal amount, enhancing layer of charcoal compactness plus hybrid, and catalysis oxidation reduces flue gas toxity,
So as to play synergistic effect with expanding fire retardant, the flame retarding and smoke suppressing properties of material are further improved.
Further, the suppression cigarette synergist uses ion-exchange by metal ion uniform load to graphene oxide table
Face.
Further, the suppression cigarette synergist carries out ion friendship under sonic oscillation and release effect while peeling off
Change, so that metal ion is loaded to surface of graphene oxide.
Above-mentioned ion-exchange includes the following steps：
1) finely dispersed graphene oxide is made in graphite oxide and deionized water under sonic oscillation and release effect
Suspension, wherein, the concentration of graphene oxide suspension is：0.0005~0.005g/mL；
2) metal salt is added in graphene oxide suspension by metering, is made scattered under sonic oscillation and release effect
Uniform mixed liquor；
3) finally mixed liquor obtained by step 2) is stirred at 30~60 DEG C to solution ph and stablizes that constant (ion exchange is thorough
Behind bottom, solution ph no longer changes, about 7), filtered, washing, the dry hydridization that graphene oxide-loaded metal ion is made
Thing.
Further, the preparation method of the hybrid comprises the following steps：
(1) graphite oxide, deionized water are added in reactor, it is 7~8 that weak base, which is added dropwise, and adjusts solution ph, in ultrasound
Vibration and the lower stripping graphite oxide of microwave heating, obtain graphene oxide suspension；
(2) metal salt is added in graphene oxide suspension by metering, continues to shell under sonic oscillation and microwave heating
From can stop obtaining mixed liquor after to suspension concentration stablizing；In whole process, pH is adjusted with weak base, controls pH=7~8；
(3) after peeling off, mixed liquor is transferred in other reactors, control temperature stirs 8~24h at 30~60 DEG C,
After stirring, filtering, after washing at least 3 times (being preferably 3~6 times), then it (is preferably 3~6 to be washed till 3 times few with organic solvent
It is secondary), 8~16h (being preferably 12h) is then dried in vacuo under 50~70 DEG C (being preferably 60 DEG C), is made graphene oxide-loaded
The hybrid of metal ion.
In step (1) and (2), the weak base is ammonium hydroxide, dimethylamine, triethylamine, aniline or pyridine；Preferably ammonium hydroxide.This
In invention, the purpose using weak base control pH=7~8 has two：First, mild alkaline conditions are conducive to graphite oxide and are easier to be filled
Divide and peel off；Second, while stripping, ammonium ion can first carry out ion exchange with hydrogen ion, be conducive in next step with metal from
Son carries out ion exchange；Because if metal ion is directly and hydrogen ion carries out ion exchange, the hydrogen ion exchanged can give birth to
Into acetic acid or nitric acid, when acetate or nitric acid salt hydrolysis, can also produce acetic acid or nitric acid, unfavorable from the perspective of chemically balancing
Metal ion in acetate or nitrate, which ionizes out, carries out ion-exchange reactions, so that ion-exchanging efficiency is limited.
Exemplified by preparing the graphene oxide hybrid of positive bivalent metal ion load, graphene oxide-loaded metal is prepared
For the principle schematic of ion hybrid as shown in fig. 6, in step 1), graphite oxide (GY100) is stripped into graphene oxide
While, hydrogen ion and the ammonium ion of surface of graphene oxide carry out equal value exchange, obtain the oxidation for having loaded ammonium ion
Graphene (GO)；In step 2), while more fully peel off, metal ion carries out equal value exchange with ammonium ion,
While graphene oxide-loaded metal ion hybrid is obtained, acetic acid ammonium salt accessory substance is produced；In step 3), 30~60
When stirring to solution ph stablizes constant at DEG C, ion exchange is properly completed.Accessory substance and miscellaneous can be removed by filtering, washing
Matter, graphene oxide-loaded metal ion hybrid is just obtained after dry.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is
The conventional products that can be obtained by commercially available purchase.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 1
1g graphite oxides (GY100) and 200mL deionized waters are added into five mouthfuls of supporting vials of ultrasonic-microwave linkage instrument
In, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, and in sonic oscillation, (ultrasonication amount is 200mL, the different change of when sonic oscillation
Width bar sends ultrasonic wave when carrying out vibrating broken, and corresponding optimal crushing is certain, this crushing is weighed with volume,
Therefore, the crushing of ultrasonic transformer and the volume of solution are identical)) and microwave heating (30 DEG C of heating-up temperature) effect lower to peel off 1.5 small
When, obtain the graphene oxide suspension that mass concentration is 0.0050g/mL；
Then 2g copper acetates are added into suspension, continue to mix when stripping 1 is small under sonic oscillation and microwave heating
Liquid, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 60 DEG C and stirs 12h, after stirring, filtering,
Washing 5 times, then washed 3 times with acetone；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded copper ion is made
Compound.Measure 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 is obtained using inductively coupled plasma atomic emission test (ICP~AES)
Arrive；Temperature corresponding to weightlessness 5% is tested to obtain using thermogravimetric analysis (TGA).
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 2
0.5g graphite oxides (GY100) and 300mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 300mL) and microwave heating (heating
40 DEG C of temperature) effect it is lower peel off 1 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0017g/mL；
Then 1.5g cobalt acetates are added into suspension, continue to mix when stripping 1 is small under sonic oscillation and microwave heating
Liquid is closed, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 50 DEG C and stirs 9h, after stirring, filtering,
Washing 5 times, then washed 4 times with ethanol；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded cobalt ions is made
Compound.Cobalt ions load capacity 0.81% is measured, temperature corresponding to weightlessness 5% is 210 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 3
1.5g graphite oxides (GY100) and 400mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, triethylamine, which is added dropwise, makes the pH value of solution heat and (add in sonic oscillation (ultrasonication amount be 400mL) and microwave 7~8
Hot 40 DEG C of temperature) effect it is lower peel off 1 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0037g/mL；
Then 1.5g nickel acetates are added into suspension, continue to obtain when stripping 0.5 is small under sonic oscillation and microwave heating
Mixed liquor, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds triethylamine until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 40 DEG C and stirs 15h, after stirring, filtering,
Washing 5 times, then washed 4 times with chloroform；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded nickel ion is made
Compound.Nickel ion load capacity 0.70% is measured, temperature corresponding to weightlessness 5% is 180 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 4
2g graphite oxides (GY100) and 500mL deionized waters are added into five mouthfuls of supporting vials of ultrasonic-microwave linkage instrument
In, aniline, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 500mL) and microwave heating (heating temperature
50 DEG C of degree) effect it is lower peel off 3 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0040g/mL；
Then 1g palladiums are added into suspension, continue to mix when stripping 1.5 is small under sonic oscillation and microwave heating
Liquid is closed, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds aniline until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 45 DEG C and stirs 8h, after stirring, filtering,
Washing 5 times, then washed 6 times with ethanol；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded palladium ion is made
Compound.Palladium ion load capacity 4.00% is measured, temperature corresponding to weightlessness 5% is 280 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 5
0.2g graphite oxides (GY100) and 400mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, dimethylamine, which is added dropwise, makes the pH value of solution heat and (add in sonic oscillation (ultrasonication amount be 400mL) and microwave 7~8
Hot 80 DEG C of temperature) effect it is lower peel off 0.5 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0005g/mL；
Then 0.4g ferric nitrates are added into suspension, continue to mix when stripping 2 is small under sonic oscillation and microwave heating
Liquid is closed, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds dimethylamine until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 30 DEG C and stirs 24h, after stirring, filtering,
Washing 5 times, then washed 5 times with ethyl acetate；Then, at 60 DEG C vacuum drying 12 it is small when, be made graphene oxide-loaded iron from
Sub- hybrid.Iron ion load capacity 1.56% is measured, temperature corresponding to weightlessness 5% is 206 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 6
0.32g graphite oxides (GY100) and 350mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 350mL) and microwave heating (heating
Temperature 60 C) effect it is lower peel off 2 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0009g/mL；
Then 0.7g copper nitrates are added into suspension, continue to mix when stripping 1 is small under sonic oscillation and microwave heating
Liquid is closed, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 50 DEG C and stirs 18h, after stirring, filtering,
Washing 5 times, then washed 3 times with ethanol；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded copper ion is made
Compound.Copper ion load capacity 1.48% is measured, temperature corresponding to weightlessness 5% is 246 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 7
1g graphite oxides (GY100) and 400mL deionized waters are added into five mouthfuls of supporting vials of ultrasonic-microwave linkage instrument
In, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 400mL) and microwave heating (heating temperature
45 DEG C of degree) effect it is lower peel off 2.5 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0025g/mL；
Then 1.5g cobalt nitrates are added into suspension, continue to mix when stripping 1 is small under sonic oscillation and microwave heating
Liquid is closed, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 35 DEG C and stirs 10h, after stirring, filtering,
Washing 5 times, then washed 4 times with acetone；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded cobalt ions is made
Compound.Cobalt ions load capacity 0.95%, temperature corresponding to weightlessness 5% are 196 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 8
0.8g graphite oxides (GY100) and 200mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 200mL) and microwave heating (heating
Temperature 70 C) effect it is lower peel off 1.5 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0040g/mL；
Then 1.6g nickel nitrates are added into suspension, continue to obtain when stripping 1.5 is small under sonic oscillation and microwave heating
Mixed liquor, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 55 DEG C and stirs 12h, after stirring, filtering,
Washing 5 times, then washed 3 times with chloroform；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded nickel ion is made
Compound.Nickel ion load capacity 1.05% is measured, temperature corresponding to weightlessness 5% is 216 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 9
1.2g graphite oxides (GY100) and 300mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 300mL) and microwave heating (heating
65 DEG C of temperature) effect it is lower peel off 1 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0040g/mL；
Then 1g palladium nitrates are added into suspension, continue to mix when stripping 2 is small under sonic oscillation and microwave heating
Liquid, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 40 DEG C and stirs 20h, after stirring, filtering,
Washing 5 times, then washed 5 times with ethyl acetate；Then, at 60 DEG C vacuum drying 12 it is small when, be made graphene oxide-loaded palladium from
Sub- hybrid.Palladium ion load capacity 3.35% is measured, temperature corresponding to weightlessness 5% is 266 DEG C.
The preparation of the graphene oxide-loaded metal ion hybrid of embodiment 10
1.4g graphite oxides (GY100) and 400mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 400mL) and microwave heating (heating
Temperature 50 C) effect it is lower peel off 2.5 it is small when, obtain the graphene oxide suspension that mass concentration is 0.0035g/mL；
Then 0.8g platinum nitrates are added into suspension, continue to mix when stripping 1 is small under sonic oscillation and microwave heating
Liquid is closed, in stripping process, measures the pH value of the mixed solution, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 40 DEG C and stirs 20h, after stirring, filtering,
Washing 5 times, then washed 6 times with acetone；Then, when vacuum drying 12 is small at 60 DEG C, it is miscellaneous that graphene oxide-loaded platinum ion is made
Compound.Platinum ion load capacity 2.47% is measured, temperature corresponding to weightlessness 5% is 259 DEG C.
Comparative example
0.3g graphite oxides (GY100) and 200mL deionized waters are added into five mouthfuls of supporting glass of ultrasonic-microwave linkage instrument
In bottle, ammonium hydroxide, which is added dropwise, makes the pH value of solution 7~8, in sonic oscillation (ultrasonication amount is 200mL) and microwave heating (heating
Temperature 50 C) effect it is lower peel off 1 it is small when, 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 it is small when obtain mixed liquor, in stripping process,
The pH value of the mixed solution is measured, if pH ＜ 7, adds ammonium hydroxide until pH is 7~8；
The mixed solution for peeling off completion is transferred in 500mL there-necked flasks at 30 DEG C and stirs 12h, after stirring, filtering,
Washing 5 times, then washed 3 times with acetone；Then, when vacuum drying 12 is small at 60 DEG C, graphene oxide is made.The institute of weightlessness 5% is right
It is 94 DEG C to answer temperature.
Graphite oxide, graphene oxide and graphene oxide-loaded copper ion hybrid (1 gained hybrid of embodiment)
Thermal weight loss contrast curve is as shown in Figure 1.As shown in Figure 1, after stripping, the heat endurance of graphene oxide is improved (higher than oxidation
Graphite), and after surface of graphene oxide has loaded copper ion, heat endurance is greatly improved.Heat endurance
Raising, be conducive to graphene oxide-loaded copper ion hybrid and be applied to high molecular material.
Embodiment 11
It is formulated according to table 1, respectively bears epoxy resin (containing curing agent), ammonium polyphosphate flame retardant (APP), graphene oxide
Copper-loaded ion hybrid (Cu2+- GO), by metered glass beaker, (about 60 DEG C) are stirred for uniformly in a heated condition,
Then pour into mould while hot to be placed in curing to obtain flame-retardant high-molecular composite material in baking oven, solidification temperature is 120 DEG C, hardening time
For 2h.
Embodiment 12~13
It is formulated according to table 1, using the method identical with embodiment 11, flame-retardant high-molecular composite material is made.
Comparative example 2
It is formulated according to table 1, using the method identical with embodiment 11, fire retarding epoxide resin is made.
Comparative example 3
It is formulated according to table 1, using the method identical with embodiment 11, the epoxy resin for being not added with fire retardant is made.
The formula table of 1 embodiment of table and comparative example flame-retardant high-molecular composite material
Note：APP --- ammonium polyphosphate flame retardant；MPP --- flame-retardants melamine Quadrafos；Cu2+~GO --- oxygen
Graphite alkene loads copper ion hybrid.In table/represent to be not added with.
Fig. 3 is the epoxy composite material (11~EP/18% of embodiment for adding graphene oxide-loaded copper ion hybrid
APP/2%Cu2+~Go) and it is not added with epoxy composite material (2~EP/ of comparative example of graphene oxide-loaded copper ion hybrid
20%APP), it is not added with the heat release of the pure epoxy resin (NeatEP) of fire retardant and graphene oxide-loaded copper ion hybrid
Rate comparison curve map.From the figure 3, it may be seen that Cu2+The addition of~GO can further reduce the heat release rate of the fire-retardant EP of APP.
Fig. 4 is the epoxy composite material (11~EP/18% of embodiment for adding graphene oxide-loaded copper ion hybrid
APP/2%Cu2+~Go) and it is not added with epoxy composite material (2~EP/ of comparative example of graphene oxide-loaded copper ion hybrid
20%APP), it is not added with the cigarette release of the pure epoxy resin (NeatEP) of fire retardant and graphene oxide-loaded copper ion hybrid
Rate comparison curve map.As shown in Figure 4, Cu2+The addition of~GO can further reduce the cigarette generating rate of the fire-retardant EP of APP.
Fig. 5 is addition and is not added with the epoxy composite material carbon monoxide release of graphene oxide-loaded copper ion hybrid
Rate comparison curve map.As shown in Figure 5, Cu2+The addition of~GO can further reduce carbon monoxide (CO) generation of the fire-retardant EP of APP
Speed.
In summary, graphene oxide-loaded metal ion hybrid is added in fire retarding epoxide resin, improves APP resistances
The fire-retardant and smoke suppressing of epoxy resin is fired, reduces the fire risk of epoxy resin.
The test result of embodiment 12 and embodiment 13 shows, with the addition of hybrid compared to being not added with the fire-retardant of hybrid
High molecular material, heat release rate reduce by 26% and 37% respectively, and cigarette generating rate reduces by 18% and 24%, carbon monoxide respectively
Generating rate reduces by 15% and 27% respectively.It can be seen from the above that graphene oxide-loaded gold is introduced in expansion type flame-retardant polymer
Belong to ion hybrid, can effectively reduce heat release rate, cigarette generating rate and the carbon monoxide generating rate of polymer.
Claims (9)
1. low-smoke and flame retardant polymer composite, it is characterised in that the composite material raw material includes：
100 parts by weight of polymeric matrix, 10~60 parts by weight of expansion type flame retardant, 0~30 parts by weight of carbon forming agent, foaming agent 0~
20 parts by weight, 0.5~5 parts by weight of suppression cigarette synergist；Wherein, the suppression cigarette synergist for surface of graphene oxide carried metal from
The hybrid of son, the load capacity for pressing down metal ion in cigarette synergist is 0.7~4%；
And the suppression cigarette synergist using ion-exchange by metal ion uniform load to surface of graphene oxide, it is described from
Sub- exchange process includes the following steps：
1) graphite oxide and deionized water are made finely dispersed graphene oxide under sonic oscillation and release effect to suspend
Liquid, wherein, the concentration of graphene oxide suspension is：0.0005~0.005g/mL；
2) by metering than metal salt is added in graphene oxide suspension, it is made scattered equal under sonic oscillation and release effect
Even mixed liquor；Wherein, the metal salt for copper acetate, cobalt acetate, nickel acetate, palladium, ferric nitrate, copper nitrate, cobalt nitrate,
Nickel nitrate, palladium nitrate or platinum nitrate；The mass ratio of the graphite oxide and metal salt is 1：0.5~3；
3) finally mixed liquor obtained by step 2) stir to solution ph at 30~60 DEG C and stablize constant, filtered, washing, do
The dry hybrid that graphene oxide-loaded metal ion is made.
2. low-smoke and flame retardant polymer composite according to claim 1, it is characterised in that the suppression cigarette synergist is weightless
5% corresponding temperature is 180~280 DEG C.
3. low-smoke and flame retardant polymer composite according to claim 1 or claim 2, it is characterised in that
The polymeric matrix be epoxy resin, polyurethane, polyethylene, polypropylene, polystyrene or polyvinyl chloride at least
It is a kind of；Or：
The expansion type flame retardant is ammonium polyphosphate, melamine polyphosphate, melamine phosphate, ammonium magnesium phosphate, boric acid
At least one of zinc, phosphate or expansible graphite；Or：
The carbon forming agent is pentaerythrite, starch, sorbierite, mannitol, phenolic resin, epoxy resin, polyurethane or triazines
At least one of carbon forming agent；Or：
The foaming agent is melamine, dicyandiamide, ammonium polyphosphate, melamine polyphosphate, melamine phosphate, boric acid
At least one of ammonium, dicyandiamide formaldehyde resin, Lauxite or polyamide.
4. low-smoke and flame retardant polymer composite according to claim 1 or claim 2, it is characterised in that the ion-exchange bag
Include following steps：
(1) graphite oxide, deionized water are added in reactor, it is 7~8 that weak base, which is added dropwise, and adjusts solution ph, in sonic oscillation
Lower stripping graphite oxide is heated with microwave, obtains graphene oxide suspension；
(2) continue to peel off under sonic oscillation and microwave heating than metal salt is added in graphene oxide suspension by metering
It can stop obtaining mixed liquor after to suspension concentration stablizing；In whole process, it is 7~8 to adjust pH with weak base；
(3) after peeling off, mixed liquor is transferred in other reactors, control temperature stirs 8~24h, stirring at 30~60 DEG C
After, filtering, after washing at least 3 times, then with organic solvent washing at least 3 times, then at 50~70 DEG C vacuum drying 8~
16h, is made the hybrid of graphene oxide-loaded metal ion.
5. low-smoke and flame retardant polymer composite according to claim 3, it is characterised in that the ion-exchange is included such as
Lower step：
(1) graphite oxide, deionized water are added in reactor, it is 7~8 that weak base, which is added dropwise, and adjusts solution ph, in sonic oscillation
Lower stripping graphite oxide is heated with microwave, obtains graphene oxide suspension；
(2) continue to peel off under sonic oscillation and microwave heating than metal salt is added in graphene oxide suspension by metering
It can stop obtaining mixed liquor after to suspension concentration stablizing；In whole process, it is 7~8 to adjust pH with weak base；
(3) after peeling off, mixed liquor is transferred in other reactors, control temperature stirs 8~24h, stirring at 30~60 DEG C
After, filtering, after washing at least 3 times, then with organic solvent washing at least 3 times, then at 50~70 DEG C vacuum drying 8~
16h, is made the hybrid of graphene oxide-loaded metal ion.
6. low-smoke and flame retardant polymer composite according to claim 4, it is characterised in that
In step (1) and (2), the microwave heating temperature is 30~80 DEG C；Or：
In step (1) and (2), the weak base is ammonium hydroxide, dimethylamine, triethylamine, aniline or pyridine；Or：
In step (3), the organic solvent is acetone, chloroform, ethanol or ethyl acetate.
7. low-smoke and flame retardant polymer composite according to claim 5, it is characterised in that
In step (1) and (2), the microwave heating temperature is 30~80 DEG C；Or：
In step (1) and (2), the weak base is ammonium hydroxide, dimethylamine, triethylamine, aniline or pyridine；Or：
In step (3), the organic solvent is acetone, chloroform, ethanol or ethyl acetate.
8. according to the low-smoke and flame retardant polymer composite of claim 6 or 7, it is characterised in that in step (1) and (2), institute
It is ammonium hydroxide to state weak base.
9. the preparation method of any one of the claim 1~8 low-smoke and flame retardant polymer composite, the method are：
When polymeric matrix is thermosetting plastics, the method is：By polymer monomer, expansion type flame retardant, carbon forming agent, foaming
Low-smoke and flame retardant polymer composite is made in agent and the synergist blending of suppression cigarette, cured reaction；
When polymeric matrix is thermoplastic, the method is：By polymeric matrix, expansion type flame retardant, carbon forming agent, foaming
Low-smoke and flame retardant polymer composite is made by the method that blended melting is kneaded in agent and suppression cigarette synergist.
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| CN111540521B (en) * | 2020-05-12 | 2022-01-07 | 陕西西特电缆有限公司 | Anti-pressure anti-interference flame-retardant composite cable |
| CN111944301A (en) * | 2020-08-05 | 2020-11-17 | 南京航空航天大学 | Flame-retardant high polymer material |
| CN116082754B (en) * | 2023-01-03 | 2024-05-03 | 万华化学集团股份有限公司 | Modified graphene oxide/hydrotalcite composite material, preparation method thereof and application thereof in flame-retardant reinforced polypropylene composite material |
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