CN106589588A - Flame-retardant enhanced-type polypropylene composite material and preparing method thereof - Google Patents
Flame-retardant enhanced-type polypropylene composite material and preparing method thereof Download PDFInfo
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Abstract
Disclosed are an flame-retardant enhanced-type polypropylene composite material and a preparing method thereof. The flame-retardant enhanced-type polypropylene composite material is prepared from a polypropylene matrix, carbon nanotube modified master batch, a potassium titanate crystal whisker, a composite fire retardant, modified filler, a compatilizer and an antioxidant, wherein the carbon nanotube modified master batch is prepared through the mixed melting of the polypropylene matrix and multiwall-carbon nanotube according to a weight ratio of 10-15:1, the composite fire retardant is a nitrogen-phosphorous composite fire retardant, through the interaction of the nitrogen-phosphorous composite fire retardant and the multiwall-carbon nanotube, a combustion decomposition product of the polypropylene composite material can generate a compact, and continuously stable char layer; meanwhile, two-mechanical melt blending of the multi-walled carbon nanotube are adopted so that the multiwall-carbon nanotube can be fully dispersed in the polypropylene matrix, and two-mechanical melt blending of the multi-walled carbon nanotube are adopted. According to the flame-retardant enhanced-type polypropylene composite material and the preparing method thereof, the operation technology is simple, the added filler causes no pollution to the environment, and thus the flame-retardant enhanced-type polypropylene composite material is environmentally friendly.
Description
Technical field
The invention belongs to polymer composites field, particularly relate to a kind of flame-retardant reinforced PP composite material and
Its preparation method.
Background technology
Polypropylene is polymerized as universal thermoplastic by propylene monomer, because its have little density, easy processing,
It is nontoxic, there are good mechanical performance, endurance surrender property and stress cracking resistance, and can reclaim and reuse, thus
The aspects such as auto industry, electrical equipment industry, article of everyday use and packaging industry have a wide range of applications.But polypropylene shrinkage factor is big, table
Face easily scratches, the fiery easy firing of easily aging, chance, and combustion process band flame is low and discharges a large amount of black smokes, and its strand contains
There is methyl, increase whole molecule chain rigidity, reduce its impact property, so as to limit use of the polypropylene material in special dimension
On the way, thus for expand polypropylene material use territory, need to be modified polypropylene process.
Polyacrylic study on the modification is done a lot of work at present, such as Application No. 201310596578.3, title
For a kind of enhancing modified polypropylene material；Application No. 201310342693.8, entitled fire-retardant enhancing polyphenylene oxide/polypropylene is closed
Golden material and preparation method thereof；Application No. 201510664437.X, entitled halogen-free flameproof long glass fiber-reinforced polypropylene is combined
Material；Application No. 201510354325.4, a kind of entitled wood powder and multi-walled carbon nano-tubes RPP resin and its system
Preparation Method etc., to find that the fire-retardant of polyacrylic composite and strengthening gets a promotion simultaneously inefficient for research by more than, this
The flame retardant effect for being primarily due to make PP composite material reach regulation must add a certain amount of fire retardant, and a certain amount of resistance
The addition of combustion agent can reduce the mechanical property of composite again, and the lifting of fire resistance and mechanical property is conflicting, to fire-retardant
Certain difficulty is brought with the research for strengthening difunctional PP composite material.
The content of the invention
The purpose of the present invention is to overcome PP composite material in prior art fire-retardant and to strengthen efficiency low, or can not be same
When have concurrently it is fire-retardant and strengthen double function characteristic problem, there is provided one kind pass through modified filler, CNT, additive and fire retardant
Compounding synergism, and then propose a kind of flame-retardant reinforced PP composite material and preparation method thereof.
The technical scheme that adopted for achieving the above object of the present invention for：
A kind of flame-retardant reinforced PP composite material, it is brilliant by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate
Palpus, compound flame retardant, modified filler, compatilizer and antioxidant are made, by weight, polypropylene matrix 50-65 parts, carbon nanometer
Pipe modified master batch 15-20 parts, potassium titanate crystal whisker 8-12 parts, compound flame retardant 10-16 parts, modified filler 10-15 parts, compatilizer 3-
5 parts and antioxidant 1-2 parts；Described modified filler compares 5 by weight:2 modified glass fibre peacekeeping modified manometer silicon dioxide
Mix；Described compound flame retardant is nitrogen phosphorus compound flame redundant, and particle diameter is 5-10 microns；Described carbon nano-tube modification
Master batch is 10-15 by weight ratio:1 polypropylene matrix and multi-walled carbon nano-tubes consolute are formed, multi-walled carbon nano-tubes Jing before consolute
Its weight 10-15% surface modifier mixed processing is crossed, described surface modifier compares 1-2 by KH550 and DOPO according to weight:
The ratio of 5-6 is mixed；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 3-4 by barium hydroxide, Sodium Chloride and KH550 according to weight:1-2:30 ratio
Mix, the modified glass-fiber is length 3mm-5mm available glass fiber and KH560, titanate coupling agent, glass dust
Compare 100 according to weight:3:2:8-10 is mixed.
Described nitrogen phosphorus compound flame redundant, wherein nitrogen content are 18-20%, and phosphorus content is 27-30%.
1-3 part white carbon blacks have been additionally added in described modified filler.
The preparation method of above-mentioned flame-retardant reinforced PP composite material, is first according to aforementioned proportion and weighs raw material and to original
Material is modified processs, then prepares carbon nano-tube modification master batch, finally by carbon nano-tube modification master batch and polypropylene matrix and
Other raw materials carry out in proportion melting mixing and product are obtained, it is characterised in that：It is described process is carried out to raw material to refer to commercially available nanometer
Silicon dioxide is mixed to get with the surface conditioning agent of its weight 3-4%, the surface conditioning agent by barium hydroxide, Sodium Chloride and
KH550 compares 3-4 according to weight:1-2:30 ratio is mixed；Length 3mm-5mm available glass fiber and KH560, titanate esters
Coupling agent, glass dust compare 100 according to weight:3:2:8-10 mixes modified glass-fiber.
Prepared by the carbon nano-tube modification master batch, multi-walled carbon nano-tubes is modified first, and its step is：(1) weigh
Multi-walled carbon nano-tubes be put in beaker, be subsequently adding 100ml volume ratios for 2:1 concentrated sulphuric acid and concentrated nitric acid mixing acid soak
24h, immersion is washed with deionized filtration after terminating, then continuously washs to neutrality, dry for standby；(2) DOPO is dried and is ground
Mill, then compares 1 with KH560 by it according to weight:1 in oil bath 180 DEG C mixed, mixing speed 600-800r/min,
Stirring 6h, is then washed with deionized 3-5 time, adds appropriate amount of deionized water and 1-1.5h is hydrolyzed under 50 DEG C of water-baths, finally
By hydrolyzate sucking filtration, and it is dried, it is standby；(3) by the product anhydrous alcohol solution in (2), mass fraction is configured to for 10-
15% ethanol solution, then according to aforementioned proportion adds multi-walled carbon nano-tubes, ultrasonic 30min, then with 80 DEG C under the conditions of it is anti-
Answer 4-4.5h, finally by product with absolute ethanol washing for several times, sucking filtration is simultaneously dried, and obtains the multi-wall carbon nano-tube of graft modification
Pipe；Then the multi-walled carbon nano-tubes of graft modification and polypropylene matrix are added into according to the above ratio pelletize in comminutor, pelletize
Machine barrel zone temperature：One 160-170 DEG C of area, 170-175 DEG C of 2nd area, 175-180 DEG C of 3rd area, 180-185 DEG C of 4th area, mold temperature is
190℃。
According to the above ratio, first by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate crystal whisker, compound flame retardant, change
Property filler, compatilizer and antioxidant add in batch mixer, mix 0.5h, then the compound of mix homogeneously is added into twin screw
Extruder, screw speed is 40～50r/min, and temperature is set in extruder barrel：One 155-160 DEG C of area, two area 165-170
DEG C, 175-180 DEG C of 3rd area, 180-185 DEG C of 4th area, compound extruded machine extrusion is obtained flame-retardant reinforced polypropylene composite materials material
Material.
In described mixing process, 1-3 part hydroxy silicon oils are additionally added in batch mixer.
In the present invention, described multi-walled carbon nano-tubes external diameter 30-50nm, internal diameter 5-12nm, length 0.5-2 μm；Described
Potassium titanate crystal whisker is Potassium Tetratitanate Whisker or crystal whisker of hexa potassium titanate average length 10-20 μm；Described compatilizer is maleic anhydride
Grafted polypropylene graft rate is 0.8-1.2%；Described antioxidant is phosphorous acids antioxidant.
In the present invention in flame-retardant reinforced PP composite material combustion process is obtained, multi-walled carbon nano-tubes can be
Mutually interspersed bridging makes composite that " class solid " behavior is presented in burning into three-dimensional net structure in polypropylene matrix, should
The presence of network structure on the one hand can polymer molecular chain always warm-up movement, improve compound system viscosity；Furthermore can be effectively
Polymer is prevented to explain the effusion of the imflammable gas to be formed and the entrance of external heat and oxygen, so as to be effectively protected base
Body, is found through experiments：Nitrogen content is 18-20% in nitrogen phosphorus compound flame redundant, many during burning when phosphorus content is 27-30%
Wall carbon nano tube makes the layer of charcoal that the catabolite of polymer is generated fine and close with compound flame retardant interaction, and layer of charcoal skeleton is strong
Degree is bigger.
Also have in prior art CNT is mixed with fire retardant composite is carried out it is fire-retardant, but in composite
Internal ignition resistant agent and multi-walled carbon nano-tubes have certain spacing distance, and cooperative flame retardant effect therebetween can not give full play to,
Directly DOPO fire retardants are grafted to into multi-walled carbon nano-tubes in the present invention, fire retardant is direct with multi-walled carbon nano-tubes in combustion process
Interact；Furthermore, the multi-walled carbon nano-tubes and filler of composite material surface have at the burning initial stage to nitrogen phosphorus compound flame retardant
Certain catalytic action, makes fire retardant decompose in advance and composite is protected, in combustion due to multi-wall carbon nano-tube
Pipe and filler effect improve the heat-transfer rate of composite, and the heat for making surface is quickly delivered to inside, reduces material surface
Heat delays the decomposition of top layer polymer, is favourable to the overall fire resistance of composite.
Filler and multi-walled carbon nano-tubes improve the compatibility of they and polymeric matrix, large-sized glass through modified
Glass fiber, the multi-walled carbon nano-tubes of middle size and whisker form 3 D stereo net with undersized nanoparticle in polymeric inner
Shape structure, when composite is subject to extraneous stress, stress is quickly delivered to composite inner and by glass by three-dimensional networking
The inserts such as glass fiber, multi-walled carbon nano-tubes, whisker and nanoparticle absorb, furthermore multi-walled carbon nano-tubes, whisker and small size
Nanoparticle can improve polyacrylic degree of crystallinity, further improve the comprehensive mechanical property of composite.
Graft modification process is carried out to multi-walled carbon nano-tubes in the present invention, its in the composite dispersibility increase,
Further to improve multi-walled carbon nano-tubes dispersibility in the composite, first by the multi-walled carbon nano-tubes of modified mistake and poly- third
Thiazolinyl body is mixed and made into multi-walled carbon nano-tubes modified master batch, then mixes modified master batch with composite again, by machine twice
Tool mixes, and in the composite dispersibility is at utmost improved to make multi-walled carbon nano-tubes.
Further, it is also possible to add a small amount of white carbon black in the composite, white carbon black can enter in composite inner to molecule
Chain plays a part of " anchor point ", to the further reinforcement of composite, while finding that product finds by burning, adds a small amount of white carbon black
Composite residues of combustion layer of charcoal is finer and close, and surface is more smooth, and the raising to the fire-retardant performance of composite is highly beneficial
's.
Furthermore, a small amount of hydroxy silicon oil can be also added during batch mixing in batch mixer, on the one hand can improve nanoparticle,
Whisker and glass fibre and polypropylene matrix and the adhesion of multi-walled carbon nano-tubes modified master batch, prevent powder particle in extrusion
Deposit in machine hopper, be so conducive to dispersion of the powder particle in polypropylene matrix, on the other hand fraction of hydroxy silicon oil exists
Be conducive to strengthening the compatibility of nanoparticle, whisker and glass fibre and polypropylene matrix in material consolute, improve they and
Adhesion between polypropylene-base body interface.
Beneficial effect：(1) in the present invention, DOPO fire retardants are directly grafted on multi-walled carbon nano-tubes, in composite
In combustion process, fire retardant and multi-walled carbon nano-tubes direct interaction give full play to cooperative flame retardant effect therebetween；Again
Multi-walled carbon nano-tubes after person's graft modification is also improved with polypropylene-base compatability, is mutually interted in polypropylene matrix
Bridging makes composite that " class solid " behavior is presented in burning into three-dimensional net structure；
(2) nitrogen phosphorus compound flame retardant is adopted in the present invention, is found by multigroup Experimental comparison, when nitrogen content is in fire retardant
18-20%, when phosphorus content is 27-30%, compound flame retardant interacts with multi-walled carbon nano-tubes and makes the combustion decomposition of polymer
The layer of charcoal that product is generated is fine and close, and layer of charcoal frame strength is bigger, and this flame retardant efficiency to composite is favourable；
(3) fully to disperse multi-walled carbon nano-tubes in polypropylene matrix, to multi-walled carbon nano-tubes using machinery twice
Melt blending, first by multi-walled carbon nano-tubes and polypropylene matrix melting mixing pelletize, then again by the multi-wall carbon nano-tube made
Pipe master batch and one piece of other fillers and polypropylene matrix consolute, through mechanical consolute twice, multi-walled carbon nano-tubes is multiple in polypropylene
Disperseed to greatest extent in condensation material；
(4) a small amount of hydroxy silicon oil can be also added during batch mixing in batch mixer, nanoparticle, crystalline substance on the one hand can be improved
Palpus and glass fibre and polypropylene matrix and the adhesion of multi-walled carbon nano-tubes modified master batch, prevent powder particle in extruder
Deposit in hopper, be so conducive to dispersion of the powder particle in polypropylene matrix, on the other hand fraction of hydroxy silicon oil is in thing
Be conducive to strengthening the compatibility of nanoparticle, whisker and glass fibre and polypropylene matrix in material consolute, improve them and gather
Adhesion between polypropylene matrix interface.
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 flame-retardant reinforced PP composite material, it is characterised in that：It is female by polypropylene matrix, carbon nano-tube modification
Grain, potassium titanate crystal whisker, compound flame retardant, modified filler, compatilizer and antioxidant are made, by weight, polypropylene matrix 50
Part, 15 parts of carbon nano-tube modification master batch, 8 parts of potassium titanate crystal whisker, 10 parts of compound flame retardant, 10 parts of modified filler, 3 parts of compatilizer and
1 part of antioxidant；Described modified filler compares 5 by weight:2 modified glass fibre peacekeeping modified manometer silicon dioxide mixing and
Into；Described compound flame retardant is nitrogen phosphorus compound flame redundant, and particle diameter is 5 microns；Described carbon nano-tube modification master batch is by weight
Amount is than being 10:1 polypropylene matrix and multi-walled carbon nano-tubes consolute are formed, and multi-walled carbon nano-tubes passes through its weight 10% before consolute
Surface modifier mixed processing, described surface modifier compares 1 by KH550 and DOPO according to weight:5 ratio is mixed；
The modified manometer silicon dioxide is that commercially available nano silicon is mixed to get with the surface conditioning agent of its weight 3%, the table
Face inorganic agent compares 3 by barium hydroxide, Sodium Chloride and KH550 according to weight:1:30 ratio is mixed, the modified glass fibre
Tie up is that length 5mm available glass fiber and KH560, titanate coupling agent, glass dust compare 100 according to weight:3:2:8 mixing and
Into.
The preparation method of above-mentioned flame-retardant reinforced PP composite material, is first according to aforementioned proportion and weighs raw material and to original
Material is modified processs, then prepares carbon nano-tube modification master batch, finally by carbon nano-tube modification master batch and polypropylene matrix and
Other raw materials carry out in proportion melting mixing and product are obtained, it is characterised in that：It is described process is carried out to raw material to refer to commercially available nanometer
Silicon dioxide is mixed to get with the surface conditioning agent of its weight 3%, the surface conditioning agent by barium hydroxide, Sodium Chloride and
KH550 compares 3 according to weight:1:30 ratio mixes modified manometer silicon dioxide；Length 5mm available glass fiber with
KH560, titanate coupling agent, glass dust compare 100 according to weight:3:2:8 mix modified glass-fiber.
Prepared by the carbon nano-tube modification master batch, multi-walled carbon nano-tubes is modified first, and its step is：(1) weigh
Multi-walled carbon nano-tubes be put in beaker, be subsequently adding 100ml volume ratios for 2:1 concentrated sulphuric acid and concentrated nitric acid mixing acid soak
24h, immersion is washed with deionized filtration after terminating, then continuously washs to neutrality, dry for standby；(2) DOPO is dried and is ground
Mill, then compares 1 with KH560 by it according to weight:1 in oil bath 180 DEG C mixed, mixing speed 600r/min, stirring
6h, is then washed with deionized 3 times, adds appropriate amount of deionized water and 1h is hydrolyzed under 50 DEG C of water-baths, finally by hydrolyzate
Sucking filtration, and be dried, it is standby；(3) by the product anhydrous alcohol solution in (2), it is configured to the ethanol that mass fraction is 10% molten
Liquid, then according to aforementioned proportion adds multi-walled carbon nano-tubes, ultrasonic 30min then to react 4h with the conditions of 80 DEG C, finally will be anti-
Answer product absolute ethanol washing for several times, sucking filtration is simultaneously dried, and obtains the multi-walled carbon nano-tubes of graft modification；Then by graft modification
The multi-walled carbon nano-tubes crossed adds according to the above ratio pelletize in comminutor, comminutor barrel zone temperature with polypropylene matrix：One area 160
DEG C, 170 DEG C of 2nd area, 175 DEG C of 3rd area, 180 DEG C of 4th area, mold temperature be 190 DEG C.
According to the above ratio, first by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate crystal whisker, compound flame retardant, change
Property filler, compatilizer and antioxidant add in batch mixer, mix 0.5h, then the compound of mix homogeneously is added into twin screw
Extruder, screw speed is 40～50r/min, and temperature is set in extruder barrel：One 155 DEG C of area, 165 DEG C of 2nd area, 3rd area
175 DEG C, 180 DEG C of 4th area, the extruded machine extrusion of compound, are obtained flame-retardant reinforced PP composite material.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described nitrogen phosphorus compound flame redundant, wherein nitrogen content are 18%, and phosphorus content is 27%；
Such as, 1 part of white carbon black has been additionally added in described modified filler；
For another example, in described mixing process, 1 part of hydroxy silicon oil is additionally added in batch mixer.
Embodiment 2
A kind of flame-retardant reinforced PP composite material, it is brilliant by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate
Palpus, compound flame retardant, modified filler, compatilizer and antioxidant are made, by weight, 55 parts of polypropylene matrix, CNT
18 parts of modified master batch, 10 parts of potassium titanate crystal whisker, 13 parts of compound flame retardant, 13 parts of modified filler, 4 parts of compatilizer and antioxidant 1
Part；Described modified filler compares 5 by weight:2 modified glass fibre peacekeeping modified manometer silicon dioxide is mixed；Described answers
It is nitrogen phosphorus compound flame redundant with fire retardant, particle diameter is 10 microns；Described carbon nano-tube modification master batch is 13 by weight ratio:1
Polypropylene matrix and multi-walled carbon nano-tubes consolute form, before consolute multi-walled carbon nano-tubes pass through its surface modifier of weight 13%
Mix, described surface modifier compares 1 by KH550 and DOPO according to weight:3 ratio is mixed；Described being modified is received
Rice silicon dioxide be that commercially available nano silicon is mixed to get with the surface conditioning agent of its weight 3%, the surface conditioning agent by
Barium hydroxide, Sodium Chloride and KH550 compare 3 according to weight:2:30 ratio is mixed, and the modified glass-fiber is length
5mm available glass fibers compare 100 with KH560, titanate coupling agent, glass dust according to weight:3:2:9 mix.
The preparation method of above-mentioned flame-retardant reinforced PP composite material, is first according to aforementioned proportion and weighs raw material and to original
Material is modified processs, then prepares carbon nano-tube modification master batch, finally by carbon nano-tube modification master batch and polypropylene matrix and
Other raw materials carry out in proportion melting mixing and product are obtained, it is characterised in that：It is described process is carried out to raw material to refer to commercially available nanometer
Silicon dioxide is mixed to get with the surface conditioning agent of its weight 3%, the surface conditioning agent by barium hydroxide, Sodium Chloride and
KH550 compares 3 according to weight:2:30 ratio is mixed；Length 5mm available glass fiber and KH560, titanate coupling agent,
Glass dust compares 100 according to weight:3:2:9 mix modified glass-fiber.
Prepared by the carbon nano-tube modification master batch, multi-walled carbon nano-tubes is modified first, and its step is：(1) weigh
Multi-walled carbon nano-tubes be put in beaker, be subsequently adding 100ml volume ratios for 2:1 concentrated sulphuric acid and concentrated nitric acid mixing acid soak
24h, immersion is washed with deionized filtration after terminating, then continuously washs to neutrality, dry for standby；(2) DOPO is dried and is ground
Mill, then compares 1 with KH560 by it according to weight:1 in oil bath 180 DEG C mixed, mixing speed 800r/min, stirring
6h, is then washed with deionized 5 times, adds appropriate amount of deionized water and 1.5h is hydrolyzed under 50 DEG C of water-baths, finally produces hydrolysis
Thing sucking filtration, and be dried, it is standby；(3) by the product anhydrous alcohol solution in (2), it is configured to the ethanol that mass fraction is 13%
Solution, then according to aforementioned proportion adds multi-walled carbon nano-tubes, ultrasonic 30min then to react 4.5h with the conditions of 80 DEG C, finally
By product with absolute ethanol washing for several times, sucking filtration is simultaneously dried, and obtains the multi-walled carbon nano-tubes of graft modification；Then will grafting
The multi-walled carbon nano-tubes being modified adds according to the above ratio pelletize in comminutor, comminutor barrel zone temperature with polypropylene matrix：One
165 DEG C of area, 175 DEG C of 2nd area, 180 DEG C of 3rd area, 185 DEG C of 4th area, mold temperature is 190 DEG C.
According to the above ratio, first by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate crystal whisker, compound flame retardant, change
Property filler, compatilizer and antioxidant add in batch mixer, mix 0.5h, then the compound of mix homogeneously is added into twin screw
Extruder, screw speed is 40～50r/min, and temperature is set in extruder barrel：One 158 DEG C of area, 168 DEG C of 2nd area, 3rd area
178 DEG C, 183 DEG C of 4th area, the extruded machine extrusion of compound, are obtained flame-retardant reinforced PP composite material.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described nitrogen phosphorus compound flame redundant, wherein nitrogen content are 20%, and phosphorus content is 28%；
Such as, 2 parts of white carbon blacks have been additionally added in described modified filler；
For another example, in described mixing process, 2 parts of hydroxy silicon oils are additionally added in batch mixer.
Embodiment 3
A kind of flame-retardant reinforced PP composite material, it is brilliant by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate
Palpus, compound flame retardant, modified filler, compatilizer and antioxidant are made, by weight, 65 parts of polypropylene matrix, CNT
20 parts of modified master batch, 12 parts of potassium titanate crystal whisker, 16 parts of compound flame retardant, 15 parts of modified filler, 5 parts of compatilizer and antioxidant 2
Part；Described modified filler compares 5 by weight:2 modified glass fibre peacekeeping modified manometer silicon dioxide composition；Described compounding resistance
Combustion agent is nitrogen phosphorus compound flame redundant, and particle diameter is 5-10 microns；Described carbon nano-tube modification master batch is 15 by weight ratio:1
Polypropylene matrix and multi-walled carbon nano-tubes consolute are formed, and multi-walled carbon nano-tubes is mixed through its surface modifier of weight 15% before consolute
Conjunction is processed, and described surface modifier compares 1 by KH550 and DOPO according to weight:3 ratio is mixed；The modified Nano
Silicon dioxide is that commercially available nano silicon is mixed to get with the surface conditioning agent of its weight 4%, and the surface conditioning agent is by hydrogen
Barium monoxide, Sodium Chloride and KH550 compare 2 according to weight:1:30 ratio is mixed, and the modified glass-fiber is length 5mm
Available glass fiber compares 100 with KH560, titanate coupling agent, glass dust according to weight:3:2:10 mix.
The preparation method of above-mentioned flame-retardant reinforced PP composite material, is first according to aforementioned proportion and weighs raw material and to original
Material is modified processs, then prepares carbon nano-tube modification master batch, finally by carbon nano-tube modification master batch and polypropylene matrix and
Other raw materials carry out in proportion melting mixing and product are obtained, it is characterised in that：It is described process is carried out to raw material to refer to commercially available nanometer
Silicon dioxide is mixed to get with the surface conditioning agent of its weight 4%, the surface conditioning agent by barium hydroxide, Sodium Chloride and
KH550 compares 2 according to weight:1:30 ratio is mixed；Length 5mm available glass fiber and KH560, titanate coupling agent,
Glass dust compares 100 according to weight:3:2:10 mix modified glass-fiber.
Prepared by the carbon nano-tube modification master batch, multi-walled carbon nano-tubes is modified first, and its step is：(1) weigh
Multi-walled carbon nano-tubes be put in beaker, be subsequently adding 100ml volume ratios for 2:1 concentrated sulphuric acid and concentrated nitric acid mixing acid soak
24h, immersion is washed with deionized filtration after terminating, then continuously washs to neutrality, dry for standby；(2) DOPO is dried and is ground
Mill, then compares 1 with KH560 by it according to weight:1 in oil bath 180 DEG C mixed, mixing speed 800r/min, stirring
6h, is then washed with deionized 5 times, adds appropriate amount of deionized water and 1.5h is hydrolyzed under 50 DEG C of water-baths, finally produces hydrolysis
Thing sucking filtration, and be dried, it is standby；(3) by the product anhydrous alcohol solution in (2), it is configured to the second that mass fraction is 10-15%
Alcoholic solution, then according to aforementioned proportion adds multi-walled carbon nano-tubes, ultrasonic 30min then to react 4.5h with the conditions of 80 DEG C, most
Afterwards by product with absolute ethanol washing for several times, sucking filtration is simultaneously dried, and obtains the multi-walled carbon nano-tubes of graft modification；Then will connect
The multi-walled carbon nano-tubes that branch was modified adds according to the above ratio pelletize in comminutor, comminutor barrel zone temperature with polypropylene matrix：
One 170 DEG C of area, 173 DEG C of 2nd area, 178 DEG C of 3rd area, 185 DEG C of 4th area, mold temperature is 190 DEG C.
According to the above ratio, first by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate crystal whisker, compound flame retardant, change
Property filler, compatilizer and antioxidant add in batch mixer, mix 0.5h, then the compound of mix homogeneously is added into twin screw
Extruder, screw speed is 40～50r/min, and temperature is set in extruder barrel：One 158 DEG C of area, 168 DEG C of 2nd area, 3rd area
180 DEG C, 185 DEG C of 4th area, the extruded machine extrusion of compound, are obtained flame-retardant reinforced PP composite material.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described nitrogen phosphorus compound flame redundant, wherein nitrogen content are 20%, and phosphorus content is 30%；
Such as, 3 parts of white carbon blacks have been additionally added in described modified filler；
For another example, in described mixing process, 3 parts of hydroxy silicon oils are additionally added in batch mixer.
Contrast test
Method according to embodiment of the present invention 1-3 prepares respectively three dimensions identical flame-retardant reinforced poly- third
Alkene composite sample, and compile be designated as sample 1, sample 2, sample 3, then using the method for the present invention prepare in addition with sample 1,
The identical flame-retardant reinforced PP composite material sample of sample 2, the dimensions of sample 3, is designated as sample 4, and sample 4 with
Being distinguished as of sample 2 does not add DOPO in the modifying agent used by multi-walled carbon nano-tubes；Sample is prepared according to the method for the present invention
The weight ratio of raw material and its filler is identical with sample 2 used in 5, and sample 5, and the difference of the two is：Multi-wall carbon nano-tube
Pipe does not have to make multi-walled carbon nano-tubes modified master batch with polypropylene matrix consolute, but directly and after unclassified stores mix homogeneously squeezes
Go out prepared final products；Sample 6 is prepared according to the method for the present invention, and sample 6 uses modified manometer silicon dioxide, but should
Modified manometer silicon dioxide compared with the method for modifying of the present invention, does not add phenol when modified.
Carry out mechanical strength under the same conditions to above sample respectively and fire resistance is determined, experimental data is as follows：
Claims (7)
1. a kind of flame-retardant reinforced PP composite material, it is characterised in that：By polypropylene matrix, carbon nano-tube modification master batch,
Potassium titanate crystal whisker, compound flame retardant, modified filler, compatilizer and antioxidant are made, by weight, polypropylene matrix 50-65
Part, carbon nano-tube modification master batch 15-20 parts, potassium titanate crystal whisker 8-12 parts, compound flame retardant 10-16 parts, modified filler 10-15
Part, compatilizer 3-5 parts and antioxidant 1-2 parts；Described modified filler compares 5 by weight:2 modified glass fibre peacekeeping is modified to be received
Rice silicon dioxide is mixed；Described compound flame retardant is nitrogen phosphorus compound flame redundant, and particle diameter is 5-10 microns；Described carbon
Nanotube modified master batch is 10-15 by weight ratio:1 polypropylene matrix and multi-walled carbon nano-tubes consolute are formed, many walls before consolute
CNT and its weight 10-15% surface modifier mixed processing, described surface modifier is by KH550 and DOPO according to weight
Amount compares 1-2:The ratio of 5-6 is mixed；The modified manometer silicon dioxide is commercially available nano silicon and its weight 3-4%
Surface conditioning agent be mixed to get, the surface conditioning agent compares 1-2 by phenol and KH550 according to weight:30 ratio mixing and
Into the modified glass-fiber is length 3mm-5mm available glass fiber and KH560, titanate coupling agent, glass dust according to weight
Amount compares 100:3:2:8-10 is mixed.
2. a kind of flame-retardant reinforced PP composite material according to claim 1, it is characterised in that：Described nitrogen phosphorus is answered
Distribution type fire retardant, wherein nitrogen content are 18-20%, and phosphorus content is 27-30%.
3. a kind of flame-retardant reinforced PP composite material according to claim 1, it is characterised in that：It is described modified to fill out
1-3 part white carbon blacks have been additionally added in material.
4. a kind of preparation method of flame-retardant reinforced PP composite material according to claim 1, is first according to above-mentioned
Ratio weighs raw material and process is modified to raw material, carbon nano-tube modification master batch is then prepared, finally by carbon nano-tube modification
Master batch carries out in proportion melting mixing and product is obtained with polypropylene matrix and other raw materials, it is characterised in that：It is described that raw material is entered
Row is processed and refers to that commercially available nano silicon is mixed to get with the surface conditioning agent of its weight 3-4%, and the surface conditioning agent is by hydrogen
Barium monoxide, Sodium Chloride and KH550 compare 3-4 according to weight:1-2:30 ratio is mixed；Length 3mm-5mm available glass is fine
Dimension compares 100 with KH560, titanate coupling agent, glass dust according to weight:3:2:8-10 mixes modified glass-fiber.
5. the preparation method of a kind of flame-retardant reinforced PP composite material according to claim 4, it is characterised in that：Institute
The preparation of carbon nano-tube modification master batch is stated, multi-walled carbon nano-tubes is modified first, its step is：（1）The many wall carbon for weighing are received
Mitron is put in beaker, is subsequently adding 100ml volume ratios for 2:1 concentrated sulphuric acid and concentrated nitric acid mixing acid soak 24h, immersion terminates
After be washed with deionized filtration, then continuously wash to neutrality, dry for standby；（2）DOPO is dried and ground, then by its with
KH560 compares 1 according to weight:1 in oil bath 180oC is mixed, mixing speed 600-800r/min, stirs 6h, Ran Houyong
Deionized water wash 3-5 time, adds appropriate amount of deionized water and 1-1.5h is hydrolyzed under 50 DEG C of water-baths, finally takes out hydrolyzate
Filter, and be dried, it is standby；（3）Will（2）In product anhydrous alcohol solution, be configured to mass fraction be 10-15% ethanol it is molten
Liquid, then according to aforementioned proportion adds multi-walled carbon nano-tubes, ultrasonic 30min then to react 4-4.5h with the conditions of 80 DEG C, finally
By product with absolute ethanol washing for several times, sucking filtration is simultaneously dried, and obtains the multi-walled carbon nano-tubes of graft modification；Then will grafting
The multi-walled carbon nano-tubes being modified adds according to the above ratio pelletize in comminutor, comminutor barrel zone temperature with polypropylene matrix：One
160-170 DEG C of area, 170-175 DEG C of 2nd area, 175-180 DEG C of 3rd area, 180-185 DEG C of 4th area, mold temperature is 190 DEG C.
6. the preparation method of a kind of flame-retardant reinforced PP composite material according to claim 4, it is characterised in that：Press
Aforementioned proportion, first by polypropylene matrix, carbon nano-tube modification master batch, potassium titanate crystal whisker, compound flame retardant, modified filler, phase
Hold agent and antioxidant is added in batch mixer, mix 0.5h, then the compound of mix homogeneously is added into double screw extruder, spiral shell
Bar rotating speed is 40 ~ 50r/min, and temperature is set in extruder barrel：One 155-160 DEG C of area, 165-170 DEG C of 2nd area, 3rd area
175-180 DEG C, 180-185 DEG C of 4th area, the extruded machine extrusion of compound, are obtained flame-retardant reinforced PP composite material.
7. the preparation method of a kind of flame-retardant reinforced PP composite material according to claim 6, it is characterised in that：Institute
In the mixing process stated, 1-3 part hydroxy silicon oils are additionally added in batch mixer.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586939A (en) * | 2018-05-24 | 2018-09-28 | 暨南大学 | A kind of environmental protection flame retardant conductive polypropylene material |
| CN109929132A (en) * | 2019-03-30 | 2019-06-25 | 裴广华 | A kind of glass fiber compound material and its processing technology of high intensity |
| CN110054835A (en) * | 2019-03-27 | 2019-07-26 | 无锡会通轻质材料股份有限公司 | A kind of preparation method of high magnification conductivity type polypropylene foaming beads |
| CN110305474A (en) * | 2019-06-21 | 2019-10-08 | 平顶山华邦工程塑料有限公司 | A kind of low temperature resistant flame retardant polyamide compoiste material and preparation method thereof |
| CN111004436A (en) * | 2019-09-29 | 2020-04-14 | 鞍钢集团矿业有限公司 | Toughened isotactic polypropylene composite material and preparation method thereof |
| CN111270423A (en) * | 2020-03-03 | 2020-06-12 | 东营俊富净化科技有限公司 | Preparation method of non-woven fabric filter material |
| CN113444318A (en) * | 2021-08-31 | 2021-09-28 | 南通伟越电器有限公司 | Preparation method of high-glossiness special material for electric appliance shell |
| CN115975295A (en) * | 2023-02-08 | 2023-04-18 | 大韩高性能材料(广东)有限公司 | High-strength high-toughness modified polypropylene nano injection molding material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328084A (en) * | 2001-07-03 | 2001-12-26 | 成都市华硕实业有限公司 | Composite of microfibre, superfine powder and polypropylene |
| CN102675895A (en) * | 2012-06-15 | 2012-09-19 | 沈阳化工大学 | Flame-retardant composite material with DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) modified nano mesoporous molecular sieve |
-
2016
- 2016-12-06 CN CN201611107748.7A patent/CN106589588A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328084A (en) * | 2001-07-03 | 2001-12-26 | 成都市华硕实业有限公司 | Composite of microfibre, superfine powder and polypropylene |
| CN102675895A (en) * | 2012-06-15 | 2012-09-19 | 沈阳化工大学 | Flame-retardant composite material with DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) modified nano mesoporous molecular sieve |
Non-Patent Citations (2)
| Title |
|---|
| 卢寿慈主编: "《粉体技术手册》", 31 July 2004, 化学工业出版社材料科学与工程出版中心 * |
| 辛菲等: "多壁碳纳米管对聚丙烯膨胀阻燃体系阻燃性能的影响", 《塑料》 * |
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|---|---|---|---|---|
| CN108586939B (en) * | 2018-05-24 | 2020-09-11 | 龙岩市润峰科技有限公司 | Environment-friendly flame-retardant conductive polypropylene material |
| CN108586939A (en) * | 2018-05-24 | 2018-09-28 | 暨南大学 | A kind of environmental protection flame retardant conductive polypropylene material |
| CN110054835A (en) * | 2019-03-27 | 2019-07-26 | 无锡会通轻质材料股份有限公司 | A kind of preparation method of high magnification conductivity type polypropylene foaming beads |
| CN110054835B (en) * | 2019-03-27 | 2022-03-29 | 无锡会通轻质材料股份有限公司 | Preparation method of high-rate conductive polypropylene foamed beads |
| CN109929132A (en) * | 2019-03-30 | 2019-06-25 | 裴广华 | A kind of glass fiber compound material and its processing technology of high intensity |
| CN109929132B (en) * | 2019-03-30 | 2022-04-15 | 浙江优为新材料有限公司 | High-strength glass fiber composite material and processing technology thereof |
| CN110305474A (en) * | 2019-06-21 | 2019-10-08 | 平顶山华邦工程塑料有限公司 | A kind of low temperature resistant flame retardant polyamide compoiste material and preparation method thereof |
| CN111004436B (en) * | 2019-09-29 | 2022-02-18 | 鞍钢集团矿业有限公司 | Toughened isotactic polypropylene composite material and preparation method thereof |
| CN111004436A (en) * | 2019-09-29 | 2020-04-14 | 鞍钢集团矿业有限公司 | Toughened isotactic polypropylene composite material and preparation method thereof |
| CN111270423A (en) * | 2020-03-03 | 2020-06-12 | 东营俊富净化科技有限公司 | Preparation method of non-woven fabric filter material |
| CN111270423B (en) * | 2020-03-03 | 2022-06-07 | 东营俊富净化科技有限公司 | Preparation method of non-woven fabric filter material |
| CN113444318A (en) * | 2021-08-31 | 2021-09-28 | 南通伟越电器有限公司 | Preparation method of high-glossiness special material for electric appliance shell |
| CN113444318B (en) * | 2021-08-31 | 2021-11-12 | 南通伟越电器有限公司 | Preparation method of high-glossiness special material for electric appliance shell |
| CN115975295A (en) * | 2023-02-08 | 2023-04-18 | 大韩高性能材料(广东)有限公司 | High-strength high-toughness modified polypropylene nano injection molding material and preparation method thereof |
| CN115975295B (en) * | 2023-02-08 | 2023-08-15 | 大韩高性能材料(广东)有限公司 | High-strength high-toughness modified polypropylene nano injection molding material and preparation method thereof |
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