CN106832504A - A kind of Graphene modified poly ethylene flame-proof composite material and preparation method thereof - Google Patents
A kind of Graphene modified poly ethylene flame-proof composite material and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Abstract
A kind of Graphene modified poly ethylene flame-proof composite material and preparation method thereof, by base polyethylene, modified graphene, silicon phosphorus compound flame retardant, synergistic reinforcement, filler, after toughener and additive are well mixed in batch mixer, final products are obtained by injection machine injection, wherein, described modified graphene is that graphene oxide is processed through hexachlorocyclotriph,sphazene, described synergistic reinforcement is mixed by CNT and modifying titanium dioxide, described filler is made up of modified glass fibre peacekeeping modified manometer silicon dioxide, by modified graphene, silicon phosphorus compound flame retardant, acted synergistically between synergistic reinforcement and filler, Graphene modified poly ethylene flame-proof composite material is obtained.Preparation process is simple of the present invention, the additive composition of use is environmentally safe, and obtained composite polyethylene material is met under the requirement of mechanical strength, has flame retardant efficiency concurrently, expands the use scope of polyethylene.
Description
Technical field
The invention belongs to polymer composites field, a kind of fire-retardant composite wood of Graphene modified poly ethylene is particularly related to
Material and preparation method thereof.
Background technology
Polyethylene has been widely used in packaging and the daily lifes such as industry, agricultural, medical treatment, health as general-purpose plastics
Every field in, be consumption is maximum in current world's macromolecular material, growth rate is a most fast class product, mainly due to
Its raw material sources is more, price is low, material property is excellent, electrical insulating property and chemical stability are good, while have be easily processed into again
The advantage of type.Although polyethylene advantage is more, also have its not enough, be mainly shown as toughness, low temperature resistant, ageing-resistant performance compared with
Difference, and molding shrinkage is big, easy firing, simultaneously because its nonpolar feature, makes it with other polar polymers, inorganic filler
Compatibility it is poor, so as to limit the application as the raw material or PP Pipe Compound of the products such as injection, fiber, film.Therefore, in order to
Expand the application field of PP, it is necessary to polyethylene is modified, its performance is improved.
Graphene as discovered in recent years two-dimentional carbon element crystal, with prominent and excellent heat conductivility and mechanical property
Can, its nanostructured is also very unique, and Graphene has larger specific surface area, and a small amount of addition just can be to polymer matrix
Body performance produces significant impact.But graphenic surface inert state again, the interface compatibility with other media is poor, and
Graphene has stronger Van der Waals force between layers, and aggregation, Graphene enhancing polymer composites are easily produced each other
The raising of performance depends on the raising of interface bond strength, and the factor of the most critical of control interface bond strength is that Graphene is entered
Row surface treatment, increases the effective functional group of graphenic surface, different functional groups is introduced by surface treatment method, so that effectively
Improve the interface cohesion of Graphene and resin.
The content of the invention
The purpose of the present invention is to overcome composite polyethylene material in the prior art fire-retardant and enhancing efficiency is low, or can not be same
When have concurrently it is fire-retardant and enhancing double function characteristic problem, there is provided one kind by modified graphene, silicon phosphorus compound flame retardant, synergistic increase
It is strong to be acted synergistically between body and filler, and then propose a kind of Graphene modified poly ethylene flame-proof composite material and preparation method thereof.
The technical scheme that is used to achieve the above object of the present invention for：
A kind of Graphene modified poly ethylene flame-proof composite material, by base polyethylene, modified graphene, silicon phosphorus compositional flame-retardant
Agent, synergistic reinforcement, filler, toughener and additive are made, by weight, base polyethylene 55-65 parts, modified graphene 3-
5 parts, 13-16 parts of silicon phosphorus compound flame retardant, 13-20 parts, filler 10-15 parts, toughener 5-8 parts and additive 1- of synergistic reinforcement
3 parts；Described modified graphene is that graphene oxide is processed through hexachlorocyclotriph,sphazene, and the two weight ratio is 1:10-15；Described
Silicon phosphorus compound flame retardant particle diameter is 5-10 microns；Described synergistic reinforcement is by CNT and modifying titanium dioxide according to weight
Than 1:10-13 is mixed, wherein, the CNT is modified multiwalled carbon nanotube, and its modification procedure is first by many walls
CNT volume ratio is 3:1 concentrated sulfuric acid and concentrated nitric acid nitration mixture immersion 24h, is washed with deionized water surface residual acid, then
With liquor potassic permanganate oxidation processes 12h, then rinsed well with deionized water, dried；Described filler compares 5 by weight:2
Modified glass fibre peacekeeping modified manometer silicon dioxide is constituted, and wherein modified glass-fiber is by available glass fiber and its weight 10-
15% surface modifier is mixed, and described surface modifier compares 1-2 by KH560 and DOPO according to weight:The ratio of 5-6 is mixed
Conjunction is formed, and the modified manometer silicon dioxide is that commercially available nano silicon mixes with the surface conditioning agent of its weight 3-4%
Arrive, the surface conditioning agent compares 1-2 by phenol and KH550 according to weight:30 ratio is mixed.
Described base polyethylene is that low density polyethylene (LDPE) and high density polyethylene (HDPE) compare 1 according to weight:3 mix.
Be placed in graphene oxide in deionized water by described modified graphene, (1), and the two ratio is 1g/10mL, ultrasound
Treatment 1h, then adjusts PH to 1-2 with diethanol amine and watery hydrochloric acid, and 48h is stirred at room temperature, then will with absolute ethyl alcohol and deionized water
Product is washed to neutrality, 50 DEG C of vacuum drying 24h；(2) dried product in (1) is taken, appropriate tetrahydrofuran is added,
Ultrasonic 1h, then stirs 1.5h, mixing speed 300-400r/min, then according to above-mentioned under the conditions of anhydrous and oxygen-free, ice-water bath
After ratio adds hexachlorocyclotriph,sphazene stirring and dissolving, 2.5 times of hexachlorocyclotriph,sphazene quality of triethylamine is added, stirs 2h,
Mixing speed 500-600r/min, is spaced 30min ultrasounds once in course of reaction；(3) after reaction terminates, centrifugation removal reaction
Liquid, with chloroform centrifuge washing 3 times to quality not reducing, then again with tetrahydrofuran centrifuge washing 3 times to mass conservation,
Finally 40 DEG C of centrifugation product is vacuum dried, modified graphene is obtained.
Described modifying titanium dioxide, takes the sodium hydroxide solution that commercially available titania powder adds concentration for 10mol/L
In, the ratio of the two is 1g/30-40mL, ultrasonic 0.5h, and gained suspension is then reacted into 6h at 160 DEG C, and reaction terminates
Afterwards, the sediment of gained is added in the deionized water of 10-15 times of its quality, suspension is formed, with the watery hydrochloric acid of 1mol/L
Solution treatment, until pH is 2.5, continues to stir 1.5-2h, and the white solid that will be obtained is washed with deionized to neutrality, finally
48h is dried in 60 DEG C of vacuum tank, modifying titanium dioxide is obtained.
Described silicon phosphorus compound flame retardant is that mass ratio is 2-3:1 ethenyl blocking siloxanes and DOPO is in reaction vessel
In, then stirring, nitrogen protection, condensing reflux, 130 DEG C of reaction 24h of constant temperature are passivated with ethyl acetate and petroleum ether, are obtained
To silicon phosphorus compound flame retardant.
The preparation method of above-mentioned Graphene modified poly ethylene flame-proof composite material, is first according to aforementioned proportion and weighs raw material simultaneously
Treatment is modified to raw material, it is mixed that modified raw material and base polyethylene and other additives are then carried out into melting in proportion
Close, obtain final Graphene modified poly ethylene flame-proof composite material, it is characterised in that：It is described that to carry out treatment to raw material refer to right
Available glass fiber is modified, and its step is：(1) DOPO is dried and is ground, it is then compared into 1- with KH560 according to weight
2:5-6 is mixed for 180 DEG C in oil bath, mixing speed 600-800r/min, stirs 6h, and 3- is then washed with deionized
5 times, appropriate amount of deionized water is added in 1-1.5h is hydrolyzed under 50 DEG C of water-baths, finally by hydrolysate suction filtration, and dry, it is standby；
(2) by the product anhydrous alcohol solution in step (1), be configured to mass fraction be 10-15% ethanol solution, then according to
Aforementioned proportion adds glass fibre, and then ultrasonic 30min reacts 4-4.5h with the conditions of 80 DEG C, finally by product nothing
Water-ethanol is washed for several times, and suction filtration is simultaneously dried, and obtains modified glass-fiber.
According to the above ratio, first by base polyethylene, modified graphene, silicon phosphorus compound flame retardant, synergistic reinforcement, fill out
Material, toughener and additive are added in batch mixer, mix 0.5h, and well mixed compound then is added into injection machine, screw rod
Rotating speed is 40~50r/min, and temperature setting is in injection machine machine barrel：One 155-160 DEG C of area, 165-170 DEG C of 2nd area, three area 175-
180 DEG C, 180-185 DEG C of 4th area, compound are molded through injection machine, final Graphene modified poly ethylene flame-proof composite material is obtained and produces
Product.
In described mixing process, 1-3 parts of dimethicone is additionally added in batch mixer.
Heretofore described multi-walled carbon nano-tubes purity is more than 95%, internal diameter：3-5nm, external diameter：8-15nm, length：
10-30μm；Described toughener is POE, and described additive is 1 by weight ratio:1 antioxidant and age resister mixing and
Into.
In the present invention, the silicon phosphorus compound flame retardant for using is for from fire retardant is developed, composite hinders during burning
- P=O ,-P-C-and-P-O-wait group to decompose rapidly in combustion agent structure, catalyzed polyethylene molecular chain rupture, and
In the form of small molecule, surface migration is thought under hot-fluid effect, softening polyvinyl thermal degradation is formed the charcoal of porous expansion
Layer, does not have drip phenomenon, under the synergy of modified graphene, the crosslink density of system after the preliminary thermal degradation of composite
Further improved with layer viscosity is softened, extend speed of the small molecule to surface migration, increase layer of charcoal void level, improve layer of charcoal
Degrees of expansion, and layer of charcoal surface compact, the continuous and derivable for being formed, can intercept external oxygen and enter and internal imflammable gas
Effusion, play good fire retardation.Furthermore, graphene oxide is by the modified ,-P-Cl bases in hexachlorocyclotriph,sphazene molecule
Mainly there is nucleophilic substitution in group, with surface of graphene oxide hydroxyl to increase surface of graphene oxide hydroxyl quantity, this hair
Bright selection monoethanolamine reacts with some epoxide groups of surface of graphene oxide in acid condition, increases graphene oxide
The hydroxyl that carbon atom is joined directly together on lamella, improves the bond strength of graphene oxide and base polyethylene.
Furthermore, glass fibre is modified, dispersiveness of the glass fibre in base polyethylene is on the one hand improved, while
The adhesion between the bond strength of glass fibre and polyethylene, the two interface of increase is improved, on the other hand fire retardant is directly connect
Branch arrives fiberglass surfacing, effect that glass fibre can be directly fire-retardant in combustion process, while can also improve top layer layer of charcoal
Consistency and adhesive force, improve the flame retardant efficiency of composite.
Using in the present invention using CNT and modifying titanium dioxide as the synergistic for coordinating anti-flammability and mechanical strength
The stress that reinforcement, CNT and modifying titanium dioxide can both have been built with additional fillers is transmitted, while can improve burned
Journey charcoal residual volume and carbon layers having thicknesses, and layer of charcoal consistency and intensity, while using method of modifying of the invention to nano-silica
Change titanium to be modified, improve dispersiveness of the nano titanium oxide in base polyethylene, and disperse more unordered, one side energy
It is enough to form cross-linked network structure in the base, in another aspect process, can be with modified graphite in the presence of shearing force
Alkene and other additives interact, and raising disperses in the base each other.
Furthermore, can add a small amount of dimethicone in mixing process, on the one hand improving mixing process, powder and short
Fibrous material and base polyethylene adhesive force, are conducive to the raising of process additive dispersiveness, while can also be as profit
Lubrication prescription is conducive to the optimization of process technological parameter, on the other hand because dimethicone has preferable heat endurance,
In combustion process, also there is certain benefit to the raising of composite polyethylene material heat endurance.
Beneficial effect：1st, graft modification treatment is carried out to glass fibre, improves glass dispersion and and polyethylene
Basal body interface bond strength, gives full play to the mechanics humidification of glass fibre, while being directly grafted in fiberglass surfacing
Fire-retardant group, effectively plays fire retardation, glass fibre is shown the double effects of fire-retardant enhancing；
2nd, the silicon phosphorus compound flame retardant used in the present invention, flame retarding efficiency is high, can be formed in composite material surface rapidly
Foamed char, under the synergy of modified graphene, in combustion process, forms the layer of charcoal of fine and close continuous and derivable, with barrier
Protective effect, furthermore glass fibre, modifying titanium dioxide also have the effect of improving to the layer of charcoal intensity of barrier action；
3rd, graphene oxide improves the group on graphene oxide layer surface by modified, increases graphene oxide
The hydroxyl that carbon atom is joined directly together on lamella, improves the bond strength of graphene oxide and base polyethylene.
4th, preparation process is simple of the present invention, the fire retardant and additive of use are Halogen product, environmentally friendly environmental pollution
It is small, furthermore composite polyethylene material can be applied to some special dimensions by product of the present invention, expand the scope of application of polyethylene.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, and raw material used is in following embodiment
The conventional raw material in this area or from can be commercially available on the market.
Embodiment 1
A kind of Graphene modified poly ethylene flame-proof composite material, it is characterised in that：By base polyethylene, modified graphene,
Silicon phosphorus compound flame retardant, synergistic reinforcement, filler, toughener and additive are made, and by weight, 55 parts of base polyethylene, change
Property 1 part of 3 parts of Graphene, 13 parts of silicon phosphorus compound flame retardant, 13 parts of synergistic reinforcement, 10 parts of filler, 5 parts of toughener and additive；
Described modified graphene is that graphene oxide is processed through hexachlorocyclotriph,sphazene, and the two weight ratio is 1:10；Described silicon phosphorus is answered
It it is 5 microns with fire retardant particle diameter；Described synergistic reinforcement compares 1 by CNT and modifying titanium dioxide according to weight:10 mix
Conjunction is formed, wherein, the CNT is modified multiwalled carbon nanotube, and its modification procedure is first by the effective body of multi-wall carbon nano-tube
Product is than being 3:1 concentrated sulfuric acid and concentrated nitric acid nitration mixture immersion 24h, is washed with deionized water surface residual acid, then molten with potassium permanganate
Liquid oxidation processes 12h, is then rinsed well with deionized water, dried；Described filler compares 5 by weight:2 modified glass-fiber
With modified manometer silicon dioxide composition, wherein modified glass-fiber is mixed by available glass fiber with its surface modifier of weight 10%
Conjunction is formed, and described surface modifier compares 1 by KH560 and DOPO according to weight:5 ratio is mixed, the modified Nano
Silica is that commercially available nano silicon is mixed to get with the surface conditioning agent of its weight 3%, and the surface conditioning agent is by benzene
Phenol and KH550 compare 1 according to weight:30 ratio is mixed.
The preparation method of above-mentioned Graphene modified poly ethylene flame-proof composite material, is first according to aforementioned proportion and weighs raw material simultaneously
Treatment is modified to raw material, it is mixed that modified raw material and base polyethylene and other additives are then carried out into melting in proportion
Close, obtain final Graphene modified poly ethylene flame-proof composite material, the described treatment that carried out to raw material refers to fine to available glass
Dimension is modified, and its step is：(1) DOPO is dried and is ground, it is then compared 1 with KH560 according to weight:5 in oil bath 180
DEG C mixed, mixing speed 600r/min, stirred 6h, be then washed with deionized 5 times, added appropriate deionization
Water finally by hydrolysate suction filtration, and is dried in 1h is hydrolyzed under 50 DEG C of water-baths, standby；(2) by the product nothing in step (1)
Water-ethanol dissolves, and is configured to the ethanol solution that mass fraction is 10%, then adds glass fibre, ultrasound according to aforementioned proportion
30min, then reacts 4h with the conditions of 80 DEG C, finally by product with absolute ethanol washing for several times, suction filtration is simultaneously dried, and is obtained
Modified glass-fiber.
According to the above ratio, first will by base polyethylene, modified graphene, silicon phosphorus compound flame retardant, synergistic reinforcement, fill out
Material, toughener and additive are added in batch mixer, mix 0.5h, and well mixed compound then is added into injection machine, screw rod
Rotating speed is 40r/min, and temperature setting is in injection machine machine barrel：One 155 DEG C of area, 165 DEG C of 2nd area, 175 DEG C of 3rd area, 180 DEG C of 4th area,
After compound is molded through injection machine, Graphene modified poly ethylene flame-proof composite material product is obtained.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described base polyethylene is that low density polyethylene (LDPE) and high density polyethylene (HDPE) compare 1 according to weight:3 mix；
Such as, described modified graphene, be placed in graphene oxide in deionized water by (1), and the two ratio is 1g/10mL,
Ultrasonically treated 1h, then adjusts PH to 1 with diethanol amine and watery hydrochloric acid, is stirred at room temperature 48h, then with absolute ethyl alcohol and deionized water
Product is washed to neutrality, 50 DEG C of vacuum drying 24h；(2) dried product in (1) is taken, appropriate tetrahydrochysene furan is added
Mutter, then ultrasonic 1h stirs 1.5h, mixing speed 300r/min under the conditions of anhydrous and oxygen-free, ice-water bath, then according to above-mentioned ratio
After example adds hexachlorocyclotriph,sphazene stirring and dissolving, 2.5 times of hexachlorocyclotriph,sphazene quality of triethylamine is added, stir 2h, stirred
Speed 500r/min is mixed, 30min ultrasounds are spaced in course of reaction once；(3) after reaction terminates, centrifugation removal reaction solution, with three
Chloromethanes centrifuge washing is not being reduced for 3 times to quality, tetrahydrofuran centrifuge washing is then used again 3 times to mass conservation, finally will
The 40 DEG C of vacuum drying of centrifugation product, obtain modified graphene；
Such as, described modifying titanium dioxide, takes commercially available titania powder and adds concentration molten for the NaOH of 10mol/L
In liquid, the ratio of the two is 1g/30mL, ultrasonic 0.5h, and gained suspension is then reacted into 6h at 160 DEG C, after reaction terminates,
The sediment of gained is added in the deionized water of 10 times of its quality, suspension is formed, at the dilute hydrochloric acid solution of 1mol/L
Reason, until pH is 2.5, continues to stir 1.5h, and the white solid that will be obtained is washed with deionized to neutrality, finally at 60 DEG C
48h is dried in vacuum tank, modifying titanium dioxide is obtained；
For another example, described silicon phosphorus compound flame retardant is that mass ratio is 2:1 ethenyl blocking siloxanes and DOPO is in reaction
In container, stirring, nitrogen protection, condensing reflux, 130 DEG C of constant temperature reacts 24h, then blunt with ethyl acetate and petroleum ether
Change, obtain silicon phosphorus compound flame retardant；
Finally, in described mixing process, 1 part of dimethicone is additionally added in batch mixer.
Embodiment 2
A kind of Graphene modified poly ethylene flame-proof composite material, by base polyethylene, modified graphene, silicon phosphorus compositional flame-retardant
Agent, synergistic reinforcement, filler, toughener and additive are made, by weight, 60 parts of base polyethylene, 4 parts of modified graphene,
2 parts of 15 parts of silicon phosphorus compound flame retardant, 17 parts of synergistic reinforcement, 13 parts of filler, 7 parts of toughener and additive；Described modified stone
Black alkene is that graphene oxide is processed through hexachlorocyclotriph,sphazene, and the two weight ratio is 1:13；Described silicon phosphorus compound flame retardant particle diameter
It is 5 microns；Described synergistic reinforcement compares 1 by CNT and modifying titanium dioxide according to weight:12 mix, wherein,
The CNT be modified multiwalled carbon nanotube, its modification procedure for first by the effective volume ratio of multi-wall carbon nano-tube be 3:1
The concentrated sulfuric acid and concentrated nitric acid nitration mixture immersion 24h, are washed with deionized water surface residual acid, then use liquor potassic permanganate oxidation processes
12h, is then rinsed well with deionized water, dried；Described filler compares 5 by weight:2 modified glass fibre peacekeeping modified Nano
Silica is constituted, and wherein modified glass-fiber is mixed by available glass fiber with its surface modifier of weight 13%, institute
The surface modifier stated compares 1 by KH560 and DOPO according to weight:3 ratio is mixed, and the modified manometer silicon dioxide is
Commercially available nano silicon is mixed to get with the surface conditioning agent of its weight 3%, and the surface conditioning agent is pressed by phenol and KH550
Compare 1 according to weight:30 ratio is mixed.
The preparation method of above-mentioned Graphene modified poly ethylene flame-proof composite material, is first according to aforementioned proportion and weighs raw material simultaneously
Treatment is modified to raw material, it is mixed that modified raw material and base polyethylene and other additives are then carried out into melting in proportion
Close, obtain final Graphene modified poly ethylene flame-proof composite material, the described treatment that carried out to raw material refers to fine to available glass
Dimension is modified, and its step is：(1) DOPO is dried and is ground, it is then compared 1 with KH560 according to weight:3 in oil bath 180
DEG C mixed, mixing speed 800r/min, stirred 6h, be then washed with deionized 5 times, added appropriate deionization
Water finally by hydrolysate suction filtration, and is dried in 1.5h is hydrolyzed under 50 DEG C of water-baths, standby；(2) product in step (1) is used
Anhydrous alcohol solution, is configured to the ethanol solution that mass fraction is 15%, then adds glass fibre, ultrasound according to aforementioned proportion
30min, then reacts 4.5h with the conditions of 80 DEG C, finally by product with absolute ethanol washing for several times, suction filtration is simultaneously dried, and is obtained
To modified glass-fiber.
According to the above ratio, first by base polyethylene, modified graphene, silicon phosphorus compound flame retardant, synergistic reinforcement, fill out
Material, toughener and additive are added in batch mixer, mix 0.5h, and well mixed compound then is added into injection machine, screw rod
Rotating speed is 50r/min, and temperature setting is in injection machine machine barrel：One 158 DEG C of area, 167 DEG C of 2nd area, 178 DEG C of 3rd area, 183 DEG C of 4th area,
Compound is molded through injection machine, and Graphene modified poly ethylene flame-proof composite material product is obtained.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described base polyethylene is that low density polyethylene (LDPE) and high density polyethylene (HDPE) compare 1 according to weight:3 mix；
Such as, described modified graphene, be placed in graphene oxide in deionized water by (1), and the two ratio is 1g/10mL,
Ultrasonically treated 1h, then adjusts PH to 1-2 with diethanol amine and watery hydrochloric acid, is stirred at room temperature 48h, then with absolute ethyl alcohol and deionization
Water washs to neutrality product, 50 DEG C of vacuum drying 24h；(2) dried product in (1) is taken, appropriate tetrahydrochysene is added
Then furans, ultrasonic 1h stirs 1.5h, mixing speed 400r/min, then according to above-mentioned under the conditions of anhydrous and oxygen-free, ice-water bath
After ratio adds hexachlorocyclotriph,sphazene stirring and dissolving, 2.5 times of hexachlorocyclotriph,sphazene quality of triethylamine is added, stirs 2h,
Mixing speed 600r/min, is spaced 30min ultrasounds once in course of reaction；(3) after reaction terminates, centrifugation removal reaction solution is used
Chloroform centrifuge washing 3 times to quality not reducing, then again with tetrahydrofuran centrifuge washing 3 times to mass conservation, finally
40 DEG C of centrifugation product is vacuum dried, modified graphene is obtained；
Such as, described modifying titanium dioxide, takes commercially available titania powder and adds concentration molten for the NaOH of 10mol/L
In liquid, the ratio of the two is 1g/35mL, ultrasonic 0.5h, and gained suspension is then reacted into 6h at 160 DEG C, after reaction terminates,
The sediment of gained is added in the deionized water of 13 times of its quality, suspension is formed, at the dilute hydrochloric acid solution of 1mol/L
Reason, until pH is 2.5, continues to stir 2h, and the white solid that will be obtained is washed with deionized to neutrality, finally true at 60 DEG C
48h is dried in empty van, modifying titanium dioxide is obtained；
For another example, described silicon phosphorus compound flame retardant is that mass ratio is 3:1 ethenyl blocking siloxanes and DOPO is in reaction
In container, stirring, nitrogen protection, condensing reflux, 130 DEG C of constant temperature reacts 24h, then blunt with ethyl acetate and petroleum ether
Change, obtain silicon phosphorus compound flame retardant；
Finally, in described mixing process, 2 parts of dimethicones are additionally added in batch mixer.
Embodiment 3
A kind of Graphene modified poly ethylene flame-proof composite material, by base polyethylene, modified graphene, silicon phosphorus compositional flame-retardant
Agent, synergistic reinforcement, filler, toughener and additive are made, by weight, 65 parts of base polyethylene, 5 parts of modified graphene,
3 parts of 16 parts of silicon phosphorus compound flame retardant, 20 parts of synergistic reinforcement, 15 parts of filler, 8 parts of toughener and additive；Described modified stone
Black alkene is that graphene oxide is processed through hexachlorocyclotriph,sphazene, and the two weight ratio is 1:15；Described silicon phosphorus compound flame retardant particle diameter
It is 10 microns；Described synergistic reinforcement compares 1 by CNT and modifying titanium dioxide according to weight:13 mix, wherein,
The CNT be modified multiwalled carbon nanotube, its modification procedure for first by the effective volume ratio of multi-wall carbon nano-tube be 3:1
The concentrated sulfuric acid and concentrated nitric acid nitration mixture immersion 24h, are washed with deionized water surface residual acid, then use liquor potassic permanganate oxidation processes
12h, is then rinsed well with deionized water, dried；Described filler compares 5 by weight:2 modified glass fibre peacekeeping modified Nano
Silica is constituted, and wherein modified glass-fiber is mixed by available glass fiber with its surface modifier of weight 15%, institute
The surface modifier stated compares 2 by KH560 and DOPO according to weight:5 ratio is mixed, and the modified manometer silicon dioxide is
Commercially available nano silicon is mixed to get with the surface conditioning agent of its weight 4%, and the surface conditioning agent is pressed by phenol and KH550
Compare 1 according to weight:15 ratio is mixed.
The preparation method of above-mentioned Graphene modified poly ethylene flame-proof composite material, is first according to aforementioned proportion and weighs raw material simultaneously
Treatment is modified to raw material, it is mixed that modified raw material and base polyethylene and other additives are then carried out into melting in proportion
Close, obtain final Graphene modified poly ethylene flame-proof composite material, the described treatment that carried out to raw material refers to fine to available glass
Dimension is modified, and its step is：(1) DOPO is dried and is ground, it is then compared 2 with KH560 according to weight:5 in oil bath 180
DEG C mixed, mixing speed 800r/min, stirred 6h, be then washed with deionized 5 times, added appropriate deionization
Water finally by hydrolysate suction filtration, and is dried in 1.5h is hydrolyzed under 50 DEG C of water-baths, standby；(2) product in step (1) is used
Anhydrous alcohol solution, is configured to the ethanol solution that mass fraction is 15%, then adds glass fibre, ultrasound according to aforementioned proportion
30min, then reacts 4.5h with the conditions of 80 DEG C, finally by product with absolute ethanol washing for several times, suction filtration is simultaneously dried, and is obtained
To modified glass-fiber.
According to the above ratio, first by base polyethylene, modified graphene, silicon phosphorus compound flame retardant, synergistic reinforcement, fill out
Material, toughener and additive are added in batch mixer, mix 0.5h, and well mixed compound then is added into injection machine, screw rod
Rotating speed is 50r/min, and temperature setting is in injection machine barrel：One 160 DEG C of area, 170 DEG C of 2nd area, 180 DEG C of 3rd area, 185 DEG C of 4th area, mix
Material is closed through injection machine, Graphene modified poly ethylene flame-proof composite material product is obtained.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described base polyethylene is that low density polyethylene (LDPE) and high density polyethylene (HDPE) compare 1 according to weight:3 mix；
Such as, described modified graphene, be placed in graphene oxide in deionized water by (1), and the two ratio is 1g/10mL,
Ultrasonically treated 1h, then adjusts PH to 2 with diethanol amine and watery hydrochloric acid, is stirred at room temperature 48h, then with absolute ethyl alcohol and deionized water
Product is washed to neutrality, 50 DEG C of vacuum drying 24h；(2) dried product in (1) is taken, appropriate tetrahydrochysene furan is added
Mutter, then ultrasonic 1h stirs 1.5h, mixing speed 400r/min under the conditions of anhydrous and oxygen-free, ice-water bath, then according to above-mentioned ratio
After example adds hexachlorocyclotriph,sphazene stirring and dissolving, 2.5 times of hexachlorocyclotriph,sphazene quality of triethylamine is added, stir 2h, stirred
Speed 600r/min is mixed, 30min ultrasounds are spaced in course of reaction once；(3) after reaction terminates, centrifugation removal reaction solution, with three
Chloromethanes centrifuge washing is not being reduced for 3 times to quality, tetrahydrofuran centrifuge washing is then used again 3 times to mass conservation, finally will
The 40 DEG C of vacuum drying of centrifugation product, obtain modified graphene；
Such as, described modifying titanium dioxide, takes commercially available titania powder and adds concentration molten for the NaOH of 10mol/L
In liquid, the ratio of the two is 1g/40mL, ultrasonic 0.5h, and gained suspension is then reacted into 6h at 160 DEG C, after reaction terminates,
The sediment of gained is added in the deionized water of 15 times of its quality, suspension is formed, at the dilute hydrochloric acid solution of 1mol/L
Reason, until pH is 2.5, continues to stir 2h, and the white solid that will be obtained is washed with deionized to neutrality, finally true at 60 DEG C
48h is dried in empty van, modifying titanium dioxide is obtained；
For another example, described silicon phosphorus compound flame retardant is that mass ratio is 3:1 ethenyl blocking siloxanes and DOPO is in reaction
In container, stirring, nitrogen protection, condensing reflux, 130 DEG C of constant temperature reacts 24h, then blunt with ethyl acetate and petroleum ether
Change, obtain silicon phosphorus compound flame retardant；
Finally, in described mixing process, 3 parts of dimethicones are additionally added in batch mixer.
Contrast test
Method according to embodiment of the present invention 1-3 prepares three identical Graphenes of dimensions and is modified poly- second respectively
Alkene flame-proof composite material sample, and volume is designated as sample 1, sample 2, sample 3, is then prepared in addition and sample using the method for the present invention
The identical Graphene modified poly ethylene flame-proof composite material sample of product 1, sample 2, the dimensions of sample 3, is designated as sample 4,
Sample 4 is distinguished as glass fibre only with KH560 treatment with sample 2, not modified with DOPO；Prepared according to the method for the present invention
Weight ratio in sample 5, and sample 5 using raw material and its filler is identical with sample 2, and the difference of the two is that sample 5 is selected
Substituted with the equal ordinary titanium dioxide of bulk density；Sample 6 is prepared according to the method for the present invention, sample 6 is distinguished as with sample 2
Middle graphene oxide is only through conventional ultrasonically treated.
Carry out mechanical strength under the same conditions to above sample respectively and combustibility is determined, experimental data is as follows：
Claims (8)
1. a kind of Graphene modified poly ethylene flame-proof composite material, it is characterised in that：By base polyethylene, modified graphene, silicon
Phosphorus compound flame retardant, synergistic reinforcement, filler, toughener and additive are made, by weight, base polyethylene 55-65 parts, change
3-5 parts of Graphene of property, 13-16 parts of silicon phosphorus compound flame retardant, 13-20 parts, filler 10-15 parts, toughener 5-8 parts of synergistic reinforcement
With additive 1-3 parts；Described modified graphene is that graphene oxide is processed through hexachlorocyclotriph,sphazene, and the two weight ratio is 1:
10-15；Described silicon phosphorus compound flame retardant particle diameter is 5-10 microns；Described synergistic reinforcement is by CNT and modified dioxy
Change titanium and compare 1 according to weight:10-13 is mixed, wherein, the CNT is modified multiwalled carbon nanotube, its modification procedure
For first by the effective volume ratio of multi-wall carbon nano-tube be 3:1 concentrated sulfuric acid and concentrated nitric acid nitration mixture immersion 24h, is washed with deionized water table
Face residual acid, then with liquor potassic permanganate oxidation processes 12h, then rinsed well with deionized water, dried；Described filler by
Weight compares 5:2 modified glass fibre peacekeeping modified manometer silicon dioxide composition, wherein modified glass-fiber is by available glass fiber
Mixed with its weight 10-15% surface modifiers, described surface modifier compares 1-2 by KH560 and DOPO according to weight:
The ratio of 5-6 is mixed, and the modified manometer silicon dioxide is at the surface of commercially available nano silicon and its weight 3-4%
Reason agent is mixed to get, and the surface conditioning agent compares 1-2 by phenol and KH550 according to weight:30 ratio is mixed.
2. a kind of Graphene modified poly ethylene flame-proof composite material according to claim 1, it is characterised in that：Described is poly-
Ethene matrix is that low density polyethylene (LDPE) and high density polyethylene (HDPE) compare 1 according to weight:3 mix.
3. a kind of Graphene modified poly ethylene flame-proof composite material according to claim 1, it is characterised in that：Described changes
The modification procedure of property Graphene is,（1）Graphene oxide is placed in deionized water, the two ratio is 1g/10mL, ultrasonically treated
1h, then adjusts PH to 1-2 with diethanol amine and watery hydrochloric acid, 48h is stirred at room temperature, then will be reacted with absolute ethyl alcohol and deionized water
Product is washed to neutrality, and 50oC is vacuum dried 24h；（2）Take（1）In dried product, add appropriate tetrahydrofuran, ultrasound
1h, then stirs 1.5h, mixing speed 300-400r/min, then according to aforementioned proportion under the conditions of anhydrous and oxygen-free, ice-water bath
After adding hexachlorocyclotriph,sphazene stirring and dissolving, 2.5 times of hexachlorocyclotriph,sphazene quality of triethylamine is added, stir 2h, stirring
Speed 500-600r/min, is spaced 30min ultrasounds once in course of reaction；（3）After reaction terminates, centrifugation removal reaction solution is used
Chloroform centrifuge washing 3 times to quality not reducing, then again with tetrahydrofuran centrifuge washing 3 times to mass conservation, finally
Product 40 will be centrifugedoC is vacuum dried, and obtains modified graphene.
4. a kind of Graphene modified poly ethylene flame-proof composite material according to claim 1, it is characterised in that：Described changes
Property titanium dioxide, take during commercially available titania powder adds concentration for the sodium hydroxide solution of 10mol/L, the ratio of the two is
1g/30-40mL, ultrasonic 0.5h, then by gained suspension 160o6h is reacted under C, after reaction terminates, by the sediment of gained
It is added in the deionized water of 10-15 times of its quality, forms suspension, is processed with the dilute hydrochloric acid solution of 1mol/L, until pH is
2.5, continue to stir 1.5-2h, the white solid that will be obtained is washed with deionized to neutrality, finally 60oIn the vacuum tank of C
48h is dried, modifying titanium dioxide is obtained.
5. a kind of Graphene modified poly ethylene flame-proof composite material according to claim 1, it is characterised in that：Described silicon
Phosphorus compound flame retardant is that mass ratio is 2-3:1 ethenyl blocking siloxanes and DOPO in reaction vessel, protect by stirring, nitrogen
Shield, condensing reflux, constant temperature 130oC reacts 24h, is then passivated with ethyl acetate and petroleum ether, obtains silicon phosphorus compositional flame-retardant
Agent.
6. a kind of preparation method of Graphene modified poly ethylene flame-proof composite material as claimed in claim 1, is first according to
The ratio of stating weighs raw material and treatment is modified to raw material, and then modified raw material is pressed with base polyethylene and other additives
Ratio carries out melting mixing, obtains final Graphene modified poly ethylene flame-proof composite material, it is characterised in that：It is described to raw material
It refers to that available glass fiber is modified to carry out treatment, and its step is：（1）DOPO is dried and ground, then by its with
KH560 compares 1-2 according to weight:5-6 is in oil bath 180oC is mixed, mixing speed 600-800r/min, stirs 6h, so
After be washed with deionized 3-5 times, appropriate amount of deionized water is added in 1-1.5h is hydrolyzed under 50 DEG C of water-baths, finally by hydrolysate
Suction filtration, and dry, it is standby；（2）By step（1）In product anhydrous alcohol solution, be configured to mass fraction for 10-15%
Ethanol solution, then adds glass fibre, ultrasonic 30min then to react 4-4.5h with the conditions of 80 DEG C, most according to aforementioned proportion
Afterwards by product with absolute ethanol washing for several times, suction filtration is simultaneously dried, and obtains modified glass-fiber.
7. a kind of preparation method of Graphene modified poly ethylene flame-proof composite material according to claim 6, its feature exists
In：According to the above ratio, first by base polyethylene, modified graphene, silicon phosphorus compound flame retardant, synergistic reinforcement, filler, toughness reinforcing
Agent and additive are added in batch mixer, mix 0.5h, and well mixed compound then is added into injection machine, and screw speed is 40
~ 50r/min, temperature setting is in injection machine machine barrel：One 155-160 DEG C of area, 165-170 DEG C of 2nd area, 175-180 DEG C of 3rd area, four
180-185 DEG C of area, after compound is molded through injection machine, is obtained final Graphene modified poly ethylene flame-proof composite material.
8. a kind of preparation method of Graphene modified poly ethylene flame-proof composite material according to claim 7, its feature exists
In：In described mixing process, 1-3 parts of dimethicone is additionally added in batch mixer.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107503123A (en) * | 2017-09-08 | 2017-12-22 | 宣城市聚源精细化工有限公司 | A kind of high-quality fire retardant |
| CN108059898A (en) * | 2018-01-24 | 2018-05-22 | 郭涛 | A kind of environment protection architecture fireproof coating and preparation method thereof |
| CN109135020A (en) * | 2018-08-31 | 2019-01-04 | 徐培培 | A method of improving high-density polyethylene plastics resistance to ag(e)ing |
| CN109148021A (en) * | 2018-09-07 | 2019-01-04 | 徐州赛欧电子科技有限公司 | A kind of flame retardant type cable |
| CN111303634A (en) * | 2020-03-27 | 2020-06-19 | 华南理工大学 | Graphene-containing halogen-free flame-retardant two-component addition type heat-conducting silicone rubber and preparation method thereof |
| CN114196187A (en) * | 2022-01-20 | 2022-03-18 | 曹苗苗 | Preparation method of graphene grafted POSS (polyhedral oligomeric silsesquioxane) synergetic flame-retardant polycarbonate composite material |
| CN114534373A (en) * | 2022-02-24 | 2022-05-27 | 江苏俊峰布业有限公司 | Nano SiO2Modified polytetrafluoroethylene dust removal filter bag and preparation method thereof |
| CN115975374A (en) * | 2023-02-20 | 2023-04-18 | 广东顾纳凯材料科技有限公司 | Flame-retardant polyolefin composite material and preparation method thereof |
| CN116675930A (en) * | 2023-08-04 | 2023-09-01 | 苏州亚通生物医疗科技有限公司 | Polypropylene material for PCR (polymerase chain reaction) plate and preparation method thereof |
| CN117304573A (en) * | 2023-09-11 | 2023-12-29 | 科迈特新材料有限公司 | High-temperature-resistant and wear-resistant auxiliary agent for rubber and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040761A (en) * | 2011-01-14 | 2011-05-04 | 华南理工大学 | High-heat-conductivity composite material and preparation method thereof |
| CN105668544A (en) * | 2016-01-19 | 2016-06-15 | 南京信息工程大学 | Oxidized multi-walled carbon nanotube preparation method |
-
2016
- 2016-12-06 CN CN201611113037.0A patent/CN106832504A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040761A (en) * | 2011-01-14 | 2011-05-04 | 华南理工大学 | High-heat-conductivity composite material and preparation method thereof |
| CN105668544A (en) * | 2016-01-19 | 2016-06-15 | 南京信息工程大学 | Oxidized multi-walled carbon nanotube preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 许佳 等: ""棉织物的六氯环三磷腈改性氧化石墨烯阻燃整理"", 《印染》 * |
| 邓利民 等: ""Si-P阻燃剂对环氧树脂热降解行为的影响"", 《材料导报B：研究篇》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107503123A (en) * | 2017-09-08 | 2017-12-22 | 宣城市聚源精细化工有限公司 | A kind of high-quality fire retardant |
| CN108059898A (en) * | 2018-01-24 | 2018-05-22 | 郭涛 | A kind of environment protection architecture fireproof coating and preparation method thereof |
| CN109135020A (en) * | 2018-08-31 | 2019-01-04 | 徐培培 | A method of improving high-density polyethylene plastics resistance to ag(e)ing |
| CN109148021A (en) * | 2018-09-07 | 2019-01-04 | 徐州赛欧电子科技有限公司 | A kind of flame retardant type cable |
| CN111303634A (en) * | 2020-03-27 | 2020-06-19 | 华南理工大学 | Graphene-containing halogen-free flame-retardant two-component addition type heat-conducting silicone rubber and preparation method thereof |
| CN114196187B (en) * | 2022-01-20 | 2023-03-28 | 福建腾博新材料科技有限公司 | Preparation method of graphene grafted POSS (polyhedral oligomeric silsesquioxane) synergetic flame-retardant polycarbonate composite material |
| CN114196187A (en) * | 2022-01-20 | 2022-03-18 | 曹苗苗 | Preparation method of graphene grafted POSS (polyhedral oligomeric silsesquioxane) synergetic flame-retardant polycarbonate composite material |
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| CN114534373B (en) * | 2022-02-24 | 2023-04-28 | 江苏俊峰布业有限公司 | Nano SiO 2 Modified polytetrafluoroethylene dust-removing filter bag and preparation method thereof |
| CN115975374A (en) * | 2023-02-20 | 2023-04-18 | 广东顾纳凯材料科技有限公司 | Flame-retardant polyolefin composite material and preparation method thereof |
| CN116675930A (en) * | 2023-08-04 | 2023-09-01 | 苏州亚通生物医疗科技有限公司 | Polypropylene material for PCR (polymerase chain reaction) plate and preparation method thereof |
| CN117304573A (en) * | 2023-09-11 | 2023-12-29 | 科迈特新材料有限公司 | High-temperature-resistant and wear-resistant auxiliary agent for rubber and preparation method thereof |
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